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WO2022044521A1 - Method for manufacturing cured product, resin composition, developing solution, method for manufacturing layered body, and method for manufacturing semiconductor device - Google Patents

Method for manufacturing cured product, resin composition, developing solution, method for manufacturing layered body, and method for manufacturing semiconductor device Download PDF

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Publication number
WO2022044521A1
WO2022044521A1 PCT/JP2021/024077 JP2021024077W WO2022044521A1 WO 2022044521 A1 WO2022044521 A1 WO 2022044521A1 JP 2021024077 W JP2021024077 W JP 2021024077W WO 2022044521 A1 WO2022044521 A1 WO 2022044521A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acid
carbon atoms
preferable
cured product
Prior art date
Application number
PCT/JP2021/024077
Other languages
French (fr)
Japanese (ja)
Inventor
和人 嶋田
敦靖 野崎
美沙樹 ▲高▼嶋
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020237000017A priority Critical patent/KR102766256B1/en
Priority to CN202180046839.7A priority patent/CN115867866A/en
Priority to JP2022545482A priority patent/JP7627700B2/en
Publication of WO2022044521A1 publication Critical patent/WO2022044521A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a method for producing a cured product, a resin composition, a developer, a method for producing a laminate, and a method for producing a semiconductor device.
  • Resins such as polyimide are applied to various applications because they have excellent heat resistance and insulating properties.
  • the application is not particularly limited, and examples thereof include semiconductor devices for mounting, such as using a pattern containing these resins as a material for an insulating film or a sealing material, or as a protective film.
  • patterns containing these resins are also used as base films and coverlays for flexible substrates.
  • a resin such as polyimide is used in the form of a resin composition containing a polyimide precursor.
  • a cured product of a polyimide precursor is formed on a substrate by applying such a resin composition onto a substrate by, for example, coating, and then subjecting it to exposure, development, modification, etc., if necessary. Can be done.
  • the resin composition can be applied by a known coating method or the like, and a fine pattern, a pattern having a complicated shape, or the like can be formed by development. It can be said that it is excellent.
  • industrial application development is expected for a method for manufacturing a cured product using a resin composition containing a polyimide precursor. ing.
  • a coating film or a molded product is formed using a negative photosensitive resin composition, the coating film or the molded product is irradiated with an electromagnetic wave in a predetermined pattern, and then the coating film on an unexposed portion is applied.
  • a method for producing a relief pattern which comprises a step of heating the coating film or a molded product before the developing step of removing and forming a pattern, wherein the heating step is a positive and continuous gas from outside the system. In an atmosphere in which volatile components generated from the coating film or the molded product are positively removed from the system, the coating film or the molded product is subjected to the heat medium or by the radiation of electromagnetic waves.
  • a method for producing a relief pattern, which is a step of heating, is described.
  • the present invention includes a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developing solution used in the method for producing the cured product, and a lamination method including the method for producing the cured product. It is an object of the present invention to provide a method for manufacturing a body, and a method for manufacturing an electronic device including the method for manufacturing the cured product or the method for manufacturing the laminate.
  • An exposure process that selectively exposes the film A developing step of developing the exposed film with a developing solution to form a pattern, and Including a modification step of modifying the above pattern,
  • the above resin is a polyimide precursor,
  • the above resin has a group that causes a reaction in which the polarity is increased by the action of an acid.
  • the content of the organic solvent with respect to the total mass of the developer is 80% by mass or more, and the content is 80% by mass or more.
  • the modification reduces the solubility of the pattern in the solvent contained in the resin composition.
  • R 1 represents a tetravalent organic group; a plurality of R 1s may be the same or different from each other; R 2 represents a divalent organic group; R 2 may be the same as or different from each other; R 3 each independently represents a hydrogen atom or an organic group.
  • ⁇ 4> The method for producing a cured product according to ⁇ 3>, wherein the repeating unit represented by the above formula (1) has a group that causes a reaction in which the polarity is increased by the action of the above acid.
  • ⁇ 5> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 4>, wherein the resin composition further contains an acid scavenger.
  • ⁇ 6> The cured product according to any one of ⁇ 1> to ⁇ 5>, wherein the developer contains 80% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameter of 8 or less. Production method.
  • RA1 to RA5 each independently represent a hydrogen atom or a monovalent organic group, and even if at least two of RA1 to RA5 are bonded to form a ring structure. Often, * represents the binding site with other structures;
  • RA6 to RA8 each independently represent a monovalent organic group, and at least two of RA6 to RA8 may be bonded to form a ring structure *.
  • ⁇ 8> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 7>, wherein the heating of the pattern is performed in the modification step.
  • ⁇ 9> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 8>, further comprising a step of heating the film after the exposure step and before the development step.
  • a method for producing a laminated body which comprises repeating the method for producing a cured product according to any one of ⁇ 1> to ⁇ 9> a plurality of times.
  • ⁇ 11> The method for producing a laminate according to ⁇ 10>, further comprising a metal layer forming step of forming a metal layer on a layer made of the cured product during a method for producing a cured product which is performed a plurality of times.
  • ⁇ 12> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 9>, or the method for producing a laminate according to ⁇ 10> or ⁇ 11>. How to manufacture electronic devices.
  • ⁇ 13> The resin composition used in the method for producing a cured product according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 14> The developer used in the method for producing a cured product according to any one of ⁇ 1> to ⁇ 9>.
  • a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developing solution used in the method for producing the cured product, and a method for producing the cured product are used.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
  • the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or.
  • Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic”, or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified.
  • GPC gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series.
  • the molecular weights shall be measured using THF (tetrahydrofuran) as an eluent.
  • NMP N-methyl-2-pyrrolidone
  • the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
  • UV rays ultraviolet rays
  • a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper”. And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C.
  • the atmospheric pressure is 101,325 Pa (1 atmospheric pressure)
  • the relative humidity is 50% RH.
  • a combination of preferred embodiments is a more preferred embodiment.
  • a resin, a compound that generates an acid by irradiation with active light or radiation hereinafter, also referred to as "photoacid generator"
  • a resin composition containing a solvent are placed on a substrate.
  • the above-mentioned resin includes a modification step of modifying a pattern, and the above-mentioned resin is a polyimide precursor, and the above-mentioned resin has a group (hereinafter, also referred to as “polarity conversion group”) that causes a reaction in which the polarity is increased by the action of an acid.
  • polarity conversion group a group that causes a reaction in which the polarity is increased by the action of an acid.
  • Negative pattern by using a film formed from a resin composition containing a polyimide precursor having a polarity converting group and a photoacid generator, and by using a developer having an organic solvent content of 80% by mass or more. Can be formed.
  • the negative pattern is a pattern in which the unexposed portion of the film is removed in the developing process. Specifically, in the exposure step, an acid is generated from the photoacid generator in the exposed part, and the polarity of the polarity converting group of the resin is increased by the action of the acid. The solubility is reduced, the exposed portion remains after the developing step, and the unexposed portion is removed.
  • the increase in the polarity suppresses the intrusion of the developer into the exposed portion, so that the swelling of the obtained pattern due to the developer is suppressed.
  • the swelling for example, when a hole pattern is formed, it is considered that an open hole pattern can be easily obtained even in a fine hole pattern.
  • a line pattern is formed by suppressing the swelling, the swelling of the line portion is suppressed and a finer line pattern is likely to be formed. That is, according to the method for producing a cured product of the present invention, it can be said that a fine pattern can be formed and the resolution is excellent.
  • the composition of the present invention is modified to reduce the solubility in the solvent contained in the resin composition, even when another resin composition is applied on the obtained pattern to form a laminated structure, the pattern is formed. Is difficult to dissolve in the resin composition, has excellent dimensional stability of the pattern of the first layer during lamination, and has excellent resolution of the pattern of the second layer during lamination, and is also excellent in formability of the laminated pattern. It is presumed.
  • Patent Document 1 a film formed from a resin composition containing a polyimide precursor having a polarity converting group and a photoacid generator is used, and the content of an organic solvent is 80% by mass or more. There is no mention of using liquid.
  • the method for producing a cured product of the present invention will be described in detail.
  • the method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a resin, a compound that generates an acid by irradiation with active light or radiation, and a solvent onto a substrate to form a film. .. Details of the resin composition used in the present invention will be described later.
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited.
  • semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film
  • a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (
  • a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable. Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
  • the shape of the base material is not particularly limited, and may be circular or rectangular. The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
  • a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used as the base material.
  • a resin composition when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
  • Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
  • the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
  • An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity.
  • the method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
  • the coating method can be appropriately selected depending on the shape of the substrate.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
  • the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
  • a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
  • EBR edge bead rinse
  • a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
  • the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
  • the drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
  • the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed by the film forming step.
  • Selective exposure means exposing a part of the film.
  • an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
  • the exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
  • the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength).
  • the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
  • the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
  • the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
  • the post-exposure heating step can be performed after the exposure step and before the developing step.
  • the heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature. Further, the heating rate may be appropriately changed during heating. Further, it is also preferable to heat the product in a hot plate, an oven, or the like that has been set to a desired temperature.
  • the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
  • the method for producing a cured product of the present invention includes a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern. By developing, the unexposed portion of the film is removed and a pattern is formed.
  • the development in which the non-exposed portion of the film is removed by the developing step is called negative type development
  • the development in which the exposed portion of the film is removed by the developing step is called positive type development.
  • the developer used in the method for producing a cured film of the present invention has an organic solvent content of 80% by mass or more with respect to the total mass of the developer.
  • the developing solution preferably contains 90% by mass or more of an organic solvent, more preferably 95% by mass or more, and further preferably 98% by mass or more, based on the total mass of the developing solution.
  • the upper limit of the content of the organic solvent is not particularly limited and may be 100% by mass.
  • the developer preferably contains 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameter of 8 or less. It is more preferable, and it is particularly preferable to contain 98% by mass or more.
  • the upper limit of the content of the organic solvent having a dH value of 8 or less is not particularly limited and may be 100% by mass.
  • the hydrogen bond term dH of the Hansen solubility parameter in an organic solvent is a value calculated using the Hansen solubility parameter software (HSPiP).
  • organic solvent examples include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • Aromatic hydrocarbons such as anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol as alcohols.
  • Methylisobutylcarbinol, triethylene glycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
  • the developer contains an organic solvent
  • one type or a mixture of two or more types of organic solvent can be used.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and ⁇ -butyrolactone are preferable.
  • a developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
  • the developer may further contain other components.
  • other components include known surfactants and known defoaming agents.
  • the method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle.
  • the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
  • the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
  • the method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate.
  • a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
  • the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
  • the developing solution is an alkaline aqueous solution
  • water can be used as the rinsing solution.
  • the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
  • the esters include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
  • alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Eth
  • Ethyl acid acid, etc. methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc.
  • ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran.
  • Ethyl Glycol Monomethyl Ether Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cycl
  • Aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols.
  • Propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
  • the rinsing liquid contains an organic solvent
  • one type or a mixture of two or more types of organic solvent can be used.
  • cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.
  • the rinsing liquid contains an organic solvent
  • 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
  • the rinse liquid may be 100% by mass of an organic solvent.
  • the rinse solution may further contain other components.
  • other components include known surfactants and known defoaming agents.
  • the method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the paddle development on the base material, the method of supplying the rinsing liquid to the base material with a shower, and the base material.
  • the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable.
  • the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
  • the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
  • a method of supplying the rinse liquid in the rinsing step a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
  • a process of vibrating with a sonic or the like and a process of combining them can be adopted.
  • the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
  • the method for producing a cured product of the present invention includes a modification step of modifying the above pattern (pattern obtained by the development step).
  • the modification step is preferably a step of imidizing the polyimide precursor in the pattern.
  • the heating of the above pattern is performed in the modification step. That is, the modification step is preferably a step of imidizing the polyimide precursor in the pattern by heating. The heating is preferably performed by the method described in the heating step below.
  • the pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step. In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
  • the heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
  • the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the resin composition of the present invention when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention.
  • the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
  • the upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step.
  • the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
  • the obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a post-development exposure step for exposing the pattern after the developing step in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like is promoted by exposure to a photobase generator or a reaction in which desorption of acid-degradable groups is promoted by exposure to a photoacid generator is promoted. can do.
  • the post-development exposure step at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
  • the post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
  • the pattern obtained by the developing step may be subjected to the metal layer forming step of forming the metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one subjected to a heating step).
  • metal layer existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing these metals are exemplified. Copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered.
  • a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
  • Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
  • Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd.
  • the method for producing a cured product of the present invention, or the cured product of the present invention is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
  • the film thickness of the cured product obtained by the method for producing the cured product of the present invention is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and more preferably 15 ⁇ m or more, for example, from the viewpoint of the insulating property of the cured product. It is preferable, and 20 ⁇ m or more is particularly preferable.
  • the upper limit of the film thickness is not particularly limited, but can be, for example, 50 ⁇ m or less. According to the method for producing a cured product of the present invention, it is possible to produce a cured product having excellent resolution even when the film thickness is relatively thick.
  • the laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
  • the laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
  • the two or more layers made of the cured product contained in the laminated body at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
  • the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.
  • the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times.
  • the preferred embodiment of the metal layer forming step is as described above.
  • a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
  • the resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing a laminated body of the present invention preferably includes a laminating step.
  • the laminating step is a process of (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step again on the surface of the pattern (resin layer) or metal layer. It is a series of steps including performing in this order. However, it may be an embodiment in which the film forming step (a) and the heating step (d) are repeated. Further, (d) the heating step may be followed by (e) a metal layer forming step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
  • the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step.
  • Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
  • the laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
  • a structure having two or more and 20 or less resin layers such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
  • the composition, shape, film thickness, etc. of each of the above layers may be the same or different.
  • a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided.
  • a film forming step an exposure step, (c) a developing step, (d) a heating step (e) a metal layer forming step are repeated in this order, or (a) film forming.
  • the step, (d) heating step, and (e) metal layer forming step are repeated in this order.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
  • the surface activation treatment step is usually performed after the metal layer forming step, but after the heating step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
  • the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the heated resin composition layer, or on the metal layer and the heated resin composition layer. For both, you may go to at least part of each.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer.
  • the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
  • the resin composition layer when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
  • Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 .
  • the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
  • the present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention.
  • the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
  • the resin composition of the present invention is a resin composition used in the method for producing a cured product of the present invention.
  • the resin composition of the present invention contains a resin, a compound that generates an acid by irradiation with active light or radiation, and a solvent.
  • the resin is a polyimide precursor, and the polarity of the resin is increased by the action of the acid. It has a group that causes a reaction.
  • the resin composition is a polyimide precursor and contains a resin having a group (polarity converting group) that causes a reaction in which the polarity is increased by the action of an acid.
  • the polar conversion group include an acid-degradable group, and a group that decomposes by the action of an acid to form an alkali-soluble group is preferable.
  • the acid-decomposable group include an acetal group, a silyl group, a silyl ether group, a tertiary alkyl ester group and the like, and an acetal group or a tertiary alkyl ester group is preferable, and an acetal group is preferable from the viewpoint of exposure sensitivity. Groups are more preferred.
  • the polarity converting group is preferably a group represented by the following formula (A-1) or the following formula (A-2).
  • RA1 to RA5 each independently represent a hydrogen atom or a monovalent organic group, and even if at least two of RA1 to RA5 are bonded to form a ring structure.
  • * represents the binding site with other structures;
  • RA6 to RA8 each independently represent a monovalent organic group, and at least two of RA6 to RA8 may be bonded to form a ring structure *. Represents a binding site with another structure.
  • RA1 and RA2 independently represent a hydrogen atom or a monovalent organic group, and a hydrogen atom or a monovalent hydrocarbon group is preferable.
  • the monovalent hydrocarbon group may be any of an aliphatic hydrocarbon group, an aromatic polyhydric group, or a group represented by a bond thereof, but is an aliphatic hydrocarbon group or an aliphatic group. It is preferably a group represented by a bond of a hydrocarbon group and an aromatic hydrocarbon group, and is a saturated aliphatic hydrocarbon group or a group represented by a bond of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group. Is preferable.
  • RA3 to RA5 independently represent a hydrogen atom or a monovalent organic group, a hydrogen atom or a monovalent hydrocarbon group is preferable, and a hydrogen atom is more preferable.
  • RA1 to RA5 when at least two of RA1 to RA5 are combined to form a ring structure, at least one of RA1 and RA2 and at least one of RA3 to RA5 are present. It is preferable to combine them to form a ring structure. Examples of the ring structure formed include a tetrahydrofuran ring and the like.
  • RA6 to RA8 independently represent a monovalent organic group, preferably a monovalent hydrocarbon group, and a monovalent hydrocarbon group having 1 to 10 carbon atoms. It is more preferable to represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, and it is particularly preferable to represent an alkyl group having 1 to 4 carbon atoms.
  • the ring structure is not particularly limited, but an aliphatic hydrocarbon ring structure is preferable, and a saturated aliphatic hydrocarbon ring structure is used. Is more preferable.
  • polyimide precursor used in the present invention preferably contains a repeating unit represented by the following formula (1).
  • R 1 represents a tetravalent organic group.
  • the plurality of R 1s may be the same as or different from each other.
  • R 2 represents a divalent organic group.
  • the plurality of R 2s may be the same as or different from each other.
  • R 3 independently represents a hydrogen atom or an organic group.
  • the repeating unit represented by the formula (1) preferably contains a polarity converting group, and at least one of the plurality of —CO 2 R 3 in the formula (1) is a group containing a polarity converting group. More preferably, at least one of the plurality of -CO 2 R 3 in the formula (1) is a group which is decomposed by the action of an acid to produce an alkali-soluble group.
  • the repeating unit represented by the above formula (1) contains a group represented by the above formula (A-1) or the above formula (A-2).
  • R 3 in the formula (1) is represented by the following formula (A'-1).
  • the repeating unit represented by the formula (1) includes the group represented by the above formula (A-1).
  • R3 in the formula (1) is the following formula (A'-2). Therefore, it is preferable that the repeating unit represented by the formula (1) contains the group represented by the above formula (A-2).
  • RA1 to RA5 are synonymous with RA1 to RA5 in the formula (A-1), respectively, and the preferred embodiments are also the same.
  • * represents a binding site with an oxygen atom to which R 3 in the formula (1) is bonded.
  • RA6 to RA8 are synonymous with RA6 to RA8 in the formula (A-2), respectively, and the preferred embodiments are also the same.
  • * represents a binding site with an oxygen atom to which R 3 in the formula (1) is bonded.
  • the resin having the repeating unit represented by the formula (1) is a resin whose solubility in an alkaline developer is increased by the action of an acid.
  • the resin having the repeating unit of the formula (1) is preferably insoluble or sparingly soluble in an alkaline developer.
  • a compound having four carboxy groups with R 1 as a nucleus, an carboxylic acid anhydride thereof, or a hydrogen atom in at least one of the above four carboxy groups is an acid. It is composed of an acid component derived from a compound substituted with a group desorbed by the action of the above, and a diamine component derived from a compound having two amino groups with R2 as a nucleus. In other words, it is represented by an acid component which is a partial structure containing the above two carbonyl groups sandwiched between the two carbonyl groups in the formula (1) and -NH-R 2 -NH- in the formula (1). It is composed of a diamine component, which is a partial structure.
  • the tetravalent organic group R1 preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. ..
  • the plurality of R 1s may be the same as or different from each other.
  • Examples of the monocyclic aromatic group in the tetravalent organic group R 1 include a benzene ring group and a pyridine ring group.
  • Examples of the fused polycyclic aromatic group in the tetravalent organic group R 1 include a naphthalene ring group and a perylene ring group.
  • Examples of the monocyclic aliphatic group in the tetravalent organic group R 1 include a cyclobutane ring group, a cyclopentane ring group, a cyclohexane ring group and the like.
  • Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R 1 include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] Oct-7-ene ring group and the like can be mentioned.
  • the tetravalent linking group having a monocyclic or fused polycyclic aliphatic group or aromatic group for the tetravalent organic group R 1 the above-mentioned monocyclic or condensed polycyclic aliphatic group or the above-mentioned monocyclic or condensed polycyclic aliphatic group or
  • the aromatic group itself may be used, but a plurality of monocyclic or fused polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group to form 4 as R1 . It may form a linking group of valences.
  • the divalent linking group is preferably an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, etc.), an oxygen atom, a sulfur atom, a divalent sulfone group, and an ester bond. , Ketone group, amide group and the like.
  • the acid component having a group derived from at least four carboxy groups with R1 as a nucleus include pyromellitic acid anhydride, 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 2, 3,3', 4'-biphenyltetracarboxylic acid anhydride, 2,2', 3,3'-biphenyltetracarboxylic acid anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid anhydride, 2 , 2', 3,3'-benzophenone tetracarboxylic acid anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride, 1,2,5,6-naphthalenetetracarboxylic acid anhydride, 2, 3,6,7-naphthalenetetracarboxylic acid anhydride, 2,3,5,6-pyridinetetracarboxylic acid anhydride, 3,
  • a component derived from pyromellitic anhydride a component derived from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 2,3,3', 4'-biphenyltetracarboxylic acid anhydride.
  • the content of the acid component derived from a compound having four carboxy groups with R1 as a core in the resin is preferably 20 to 70 mol%, preferably 30 to 70 mol% with respect to all the repeating units constituting the resin. More preferably, it is 60 mol%.
  • R 2 in the formula (1) represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
  • a cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group.
  • Preferred embodiments of the present invention exemplify the groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably the groups represented by -Ar-L-Ar-.
  • Ar is an aromatic group independently
  • L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-,. -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
  • R 2 is preferably derived from diamine.
  • the diamine used for producing the resin include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group.
  • groups containing aromatic groups include:
  • O)-, -S-, -SO 2- , NHCO-, or a group selected from a combination thereof is preferable, and it is a single bond or a group having 1 to 3 carbon atoms which may be substituted with a fluorine atom.
  • * represents a binding site with another structure.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
  • a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
  • R2 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
  • Ar is an aromatic group independently
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or SO2-.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 2 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance.
  • a divalent organic group represented by the formula (61) is more preferable.
  • Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group. * Represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
  • R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group. * Represents a binding site with another structure.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
  • a silicon diamine component can be used as the diamine component having R 2 as a core.
  • examples of this are bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, and bis ( ⁇ -aminopropyl) tetramethyl.
  • Examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
  • a disiloxane component a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
  • a disiloxane component examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyld
  • R 5 and R 6 represent a divalent organic group
  • R 7 and R 8 each independently represent a monovalent organic group. That is, the plurality of R 7s may be the same or different from each other.
  • the plurality of R8s may be the same as or different from each other.
  • Examples of the divalent organic group represented by R5 and R6 include a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, a phenylene group having 6 to 20 carbon atoms, and carbon. It represents a divalent alicyclic group of the number 3 to 20, or a group composed of a combination thereof.
  • the monovalent organic group represented by R 7 and R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. .. More specifically, the following can be mentioned.
  • At least one of the plurality of -CO 2 R 3 present in the resin is a group that is decomposed by the action of an acid to produce an alkali-soluble group.
  • a group that decomposes by the action of an acid to produce an alkali-soluble group is a group that decomposes by the action of an acid and produces an alkali-soluble group such as a hydroxy group (for example, a phenolic hydroxy group) or a carboxy group on the resin side (hereinafter referred to as a group).
  • the acid-degradable group is preferably a group that is decomposed by the action of an acid to generate a carboxy group as an alkali-soluble group on the resin side.
  • a preferred group as an acid-degradable group is a group in which the hydrogen atom of these alkali-soluble groups is replaced with a group that desorbs an acid. Examples of the group desorbed by the acid include -C (R 36 ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), and -C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be coupled to each other to form a ring.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • the alkyl group may be linear or branched.
  • a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
  • the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
  • As the aralkyl group an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
  • the above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the acid-degradable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group or the like. More preferably, it is a tertiary alkyl ester group or an acetal ester group, and by using this, a photosensitive film having high sensitivity and high resolution can be obtained.
  • the tertiary alkyl ester group as the acid-degradable group is preferably an ester group in which the hydrogen atom of the carboxy group is substituted with a group represented by the following formula (AI).
  • T represents a single bond or * -Rt-COO- # (* is synonymous with * in the formula (AI), and # represents a binding site with a carbon atom bonded to Rx 1 to Rx 3 ).
  • Rt represents an alkylene group or a cycloalkylene group.
  • Rx 1 to Rx 3 independently represent a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx 1 to Rx 3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).
  • * represents a binding site with another structure.
  • Alkyl groups represented by Rx 1 to Rx 3 include carbons such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group, octyl group and dodecyl group.
  • An alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • Examples of the cycloalkyl group represented by Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cyclo such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Alkyl groups are preferred.
  • Examples of the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl. Polycyclic cycloalkyl groups such as groups are preferred. A monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferable. In the formula (AI), it is preferable that Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
  • a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetra
  • Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (1 to 4 carbon atoms), and a polyalkylene group. Examples thereof include an oxy group, a carboxy group and an alkoxycarbonyl group (2 to 6 carbon atoms), and a carbon number of 20 or less is preferable.
  • Rxa and Rxb each represent an alkyl group having 1 to 6 carbon atoms.
  • Z represents a substituent that each of the above groups may have, and when a plurality of these groups are present, they are independent of each other.
  • p represents 0 or a positive integer. * Represents a binding site with another structure.
  • the tertiary alkyl ester group as an acid-degradable group is, as a group represented by the formula (AI), at least one of a group represented by the following formula (I) and a group represented by the following formula (II). It is more preferable that it is a tertiary alkyl ester group having.
  • R 2 , R 4 , R 5 , and R 6 each independently represent an alkyl group or a cycloalkyl group.
  • R represents an atomic group required to form an alicyclic structure together with a carbon atom. * Represents a binding site with another structure.
  • the alkyl group in R2 may be a linear type or a branched type, and may have a substituent.
  • the cycloalkyl group in R2 may be monocyclic or polycyclic, and may have a substituent.
  • R2 is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.
  • R represents an atomic group required to form an alicyclic structure together with carbon atoms.
  • the alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and more preferably a hydrocarbon ring structure.
  • the alicyclic structure or the hydrocarbon ring structure of the single ring preferably has 3 to 8 carbon atoms, and more preferably 5 or 6 carbon atoms.
  • the alkyl group in R 4 , R 5 and R 6 may be a linear type or a branched type, and may have a substituent.
  • the alkyl group preferably has 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and a hexyl group.
  • the cycloalkyl group in R 4 , R 5 , and R 6 may be monocyclic or polycyclic, and may have a substituent.
  • a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group
  • a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group is preferable.
  • Examples of the group represented by the formula (I) include the groups represented by the following formulas (Ia) and (Ib).
  • R 2 is synonymous with R 2 in the formula (I). * Represents a binding site with another structure.
  • the group represented by the formula (II) is a group represented by the following formula (II-a).
  • R4 and R5 are synonymous with those in formula ( II). * Represents a binding site with another structure.
  • the acetal ester group as the acid-degradable group is preferably an ester group in which the hydrogen atom of the carboxy group is substituted with the group represented by the following formula (III).
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • Rb represents a single bond or a divalent linking group.
  • Q represents an alkyl group, an alicyclic group which may contain a heteroatom, or an aromatic ring group which may contain a heteroatom.
  • At least two of Ra, Rb and Q may be coupled to each other to form a ring. This ring is preferably a 5-membered ring or a 6-membered ring. * Represents a binding site with another structure.
  • Ra examples include the same as the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group for R36.
  • Ra may be a group represented by the following formula (IV) or (V) from the viewpoint that decomposition of the acetal ester group as an acid-decomposable group during storage can be suppressed by steric hindrance and deterioration of patterning property is prevented. preferable.
  • Rc, Rd, Re, Rf and Rg are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group and a cyano group.
  • it represents a halogen atom
  • Rc and Rd may be bonded to each other to form a ring, or at least two of Re, Rf and Rg may be bonded to each other to form a ring.
  • Ra is a group represented by the formula (IV) or the formula (V)
  • the progress of the imidization reaction during storage can be suppressed in the resin having the repeating unit represented by the formula (1), and the patterning property can be improved. It is possible to prevent the decrease.
  • the alkyl group, cycloalkyl group, aryl group, or aralkyl group as Rc, Rd, Re, Rf, Rg is the same as the above-mentioned alkyl group, cycloalkyl group, aryl group, aralkyl group for R36. Things can be mentioned.
  • alkoxy group as Rc, Rd, Re, Rf, Rg an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
  • the alkyl base portion of the alkoxy group may be linear, branched or cyclic, or may be a combination thereof.
  • aryloxy group as Rc, Rd, Re, Rf and Rg an aryloxy group having 6 to 10 carbon atoms is preferable, and specific examples thereof include phenoxy, toluyloxy and 1-naphthoxy.
  • alkoxycarbonyl group as Rc, Rd, Re, Rf, Rg an alkoxycarbonyl group having 1 to 10 carbon atoms is preferable, and specifically, methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, Cyclohexyloxycarbonyl and the like can be mentioned.
  • Examples of the aryloxy moiety of the aryloxycarbonyl group as Rc, Rd, Re, Rf and Rg include those similar to the above-mentioned aryloxy group.
  • At least one of Rc and Rd in the formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, and the like. It is preferably an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and more preferably at least one is an aryl group.
  • the divalent linking group as Rb is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group.
  • a cycloalkylene group having 3 to 15 carbon atoms for example, a cyclopentylene group or a cyclohexylene group
  • R 0 is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and the like. Hexyl group, octyl group, etc.).
  • Rb is preferably a single bond, an alkylene group, or a divalent linking group consisting of a combination of an alkylene group and at least one of -O-, -CO-, -CS- and -N (R 0 )-, and a single bond is preferable.
  • An alkylene group, or a divalent linking group consisting of a combination of an alkylene group and —O— is more preferred.
  • R 0 is synonymous with the above-mentioned R 0 .
  • the alkyl group as Q is, for example, the same as the above-mentioned alkyl group as Ra.
  • Examples of the alicyclic group and aromatic ring group as Q include the cycloalkyl group and aryl group as Ra described above. Its carbon number is preferably 3 to 18.
  • a group in which a plurality of aromatic rings are linked via a single bond is also included in the aromatic group as Q.
  • Examples of the alicyclic group containing a heteroatom and the aromatic ring group containing a heteroatom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole and thiazole. And pyrrolidone.
  • the alicyclic group and the aromatic ring group as Q may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group and an alkoxycarbonyl group. Can be mentioned.
  • (-Rb-Q) is a methyl group, an aryloxyethyl group, a cyclohexylethyl group or an arylethyl group, which improves solubility and thermal stability.
  • Ra, Rb and Q are bonded to each other to form a ring
  • any of Rb and Q and Ra are bonded to form a propylene group or a butylene group and contain an oxygen atom.
  • the case of forming a 5-membered ring or a 6-membered ring may be mentioned.
  • NC When the total number of carbon atoms of Ra, Rb and Q is expressed as NC, when NC is large, the change in the alkali dissolution rate of the resin becomes large before and after the group represented by the formula (III) is eliminated. The dissolution contrast becomes hard and the resolution is improved.
  • the range of NC is preferably 2 to 20, and particularly preferably 2 to 15. When NC is 20 or less, the decrease in the glass transition temperature of the polymer compound is suppressed, and the formation of defects in which desorbed substances from acid-degradable groups adhere to the pattern is suppressed.
  • At least one of Ra, Rb and Q is an electron-withdrawing group or a group having an electron-withdrawing group.
  • the electron-attracting group include an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxy group and a nitrile group (cyano group).
  • An alkylsulfonyl group, an arylsulfonyl group, a nitro group and the like, and an alkoxy group, an aryl group, an acyl group and the like are preferable.
  • the thermal decomposition temperature of —CO 2 R 3 in the formula (1) is preferably 100 to 220 ° C, more preferably 120 to 210 ° C, and particularly preferably 140 to 200 ° C.
  • the pyrolysis temperature can be determined, for example, from differential thermal balance analysis. When the thermal decomposition temperature is at least the above lower limit, the storage stability of the resin composition of the present invention is improved. Further, when the thermal decomposition temperature is not more than the above upper limit, the exposure sensitivity of the resin composition of the present invention is improved.
  • At least one of Rx 1 to Rx 3 in the above formula (A1) is a group represented by the following formula (VI).
  • Examples thereof include a certain structure, a structure in which Ra in the above formula (III) is a group represented by the above formula (IV) or the following formula (VII).
  • R 7 to R 8 independently represent a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic), and at least R 7 to R 8 are represented.
  • One is a hydrogen atom.
  • * Represents a binding site with another structure.
  • Rh represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
  • * Represents a binding site with another structure.
  • Specific examples of the alkyl group and cycloalkyl group for R 7 to R 8 preferred examples include the alkyl group for Rx 1 to Rx 3 , and the above-mentioned specific examples and preferred examples of the cycloalkyl group. ..
  • alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rh include the same as the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group for R36 .
  • alkoxy group as Rh an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
  • the alkyl base portion of the alkoxy group may be linear, branched or cyclic, or may be a combination thereof.
  • aryloxy group as Rh an aryloxy group having 6 to 10 carbon atoms is preferable, and specific examples thereof include phenoxy, toluyloxy, 1-naphthoxy and the like.
  • the alkoxycarbonyl group as Rh is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like.
  • Examples of the aryloxy moiety of the aryloxycarbonyl group as Rh include the same as the above-mentioned aryloxy group.
  • R 3 in the formula (1) may be an organic group different from the group which is decomposed by the action of an acid to form an alkali-soluble group.
  • Such an organic group can be used without particular limitation as long as the effect of the present invention can be obtained, but it may be a linear or branched alkyl group, a cycloalkyl group, an aryl group, or a polyalkyleneoxy. The group etc. can be mentioned. Preferred embodiments of these groups are similar to the preferred embodiments of these groups in R36 described above.
  • a hydrogen atom and an organic group can be mixed in R3.
  • the ratio of the organic group to the total R 3 in the resin is preferably 100 mol% to 20 mol%, and the ratio of the organic group is more preferably 100 mol% to 40 mol%.
  • the dissolution rate in an alkaline aqueous solution changes, and this adjustment makes it possible to obtain a resin composition having an appropriate dissolution rate.
  • the ratio of the groups decomposed by the action of an acid to produce an alkali-soluble group, the so-called protection rate is preferably 40 to 100%, preferably 45 to 100%. Is more preferable.
  • the terminal encapsulant can be reacted with the end of the polymer containing the repeating unit represented by the formula (1) as a main component.
  • the terminal encapsulant monoalcohol, phenol, thiol, thiophenol, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.
  • the number of repetitions of the repetition unit that is, the molecular weight can be controlled within a preferable range, which is preferable.
  • the terminal encapsulant can suppress acid deactivation due to neutralization of the terminal amine and the generated acid.
  • various organic groups such as a cross-linking reactive group having a carbon-carbon unsaturated bond can be introduced as the terminal group.
  • Examples of the monoalcohol used for the terminal encapsulant include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol and the like.
  • Examples thereof include secondary alcohols such as class alcohols, isopropanols, 2-butanols, cyclohexyl alcohols, cyclopentanols and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohols and adamantan alcohols.
  • Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
  • the monoamines used in the terminal encapsulants are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-. 6-Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene
  • 5-amino-8-hydroxyquinoline 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amin
  • Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as terminal encapsulants are phthalic acid anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride.
  • Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxylene Naphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto -3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenes
  • Dicarboxylic acid 3-hydroxyphthalic acid, 5-norbornen-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboki Cinaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene , A monoacid chloride compound in which only the monocarboxy group of dicarboxylic acids such as 2,7-dicarboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples thereof include active ester compounds obtained by reaction with dicarboxyimide.
  • acid anhydrides such as phthalic acid anhydride, maleic acid anhydride, nagic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol , 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-dietinylbenzoic acid, 3,5-diethynyl Monocarboxylic acids such as benzoic acid,
  • Monoacid chloride compounds in which only the monocarboxy group of dicarboxylic acids such as naphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene are acid chlorides, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy
  • An active ester compound obtained by reaction with -5-norbornen-2,3-dicarboxyimide is preferable.
  • the introduction ratio of the monoamine used in the terminal encapsulant is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol% with respect to the total amine component.
  • the introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the terminal encapsulant is in the range of 0.1 to 100 mol% with respect to the diamine component. It is preferable, and particularly preferably 5 to 90 mol%.
  • a plurality of different end groups may be introduced by reacting a plurality of end sealants.
  • the terminal sealant introduced into the polymer can be easily detected by the following method.
  • the polymer into which the terminal encapsulant has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer.
  • GC gas chromatography
  • NMR NMR
  • the terminal encapsulant can be easily detected.
  • the polymer component into which the terminal encapsulant has been introduced can be easily detected by directly measuring the pyrolysis gas chromatograph (PGC), the infrared spectrum, and the 13 CNMR spectrum.
  • PPC pyrolysis gas chromatograph
  • the specific resin used in the resin composition of the present invention preferably contains a repeating unit represented by the formula (1) as a main component.
  • the main component referred to here means that it contains 70 mol% or more of the repeating unit represented by the formula (1). It is more preferably 80 mol% or more, and most preferably 90 mol% or more.
  • the specific resin used in the present invention may be a copolymer of a repeating unit represented by the formula (1) and another repeating unit, or may contain a plurality of repeating units represented by the formula (1). It may be a mixture of the resins of.
  • the resin containing the repeating unit represented by the formula (1) and the resin not containing the repeating unit represented by the formula (1) are decomposed into R3 by the action of an acid. It may be a mixture with a resin that does not have a group that produces an alkali-soluble group).
  • the resin containing the repeating unit represented by the formula (1) is preferably contained in an amount of 50% by mass or more, more preferably 75% by mass or more.
  • the type and amount of the repeating unit used for the copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.
  • the resin containing the repeating unit represented by the formula (1) preferably has a mass average molecular weight of 200,000 or less, preferably 1,000 to 200,000, from the viewpoint of alkali dissolution rate, film physical characteristics, and the like. It is preferable, more preferably 2,000 to 100,000, and particularly preferably 3,000 to 100,000. By setting this molecular weight range, it is possible to obtain a photosensitive film having low stress, excellent mechanical properties, and excellent resolution with few development defects.
  • the degree of dispersion (molecular weight distribution) is preferably 1.0 to 7.0, more preferably 1.5 to 6.5. In the present specification, the degree of dispersion is a value calculated by weight average molecular weight / number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one specific resin are within the above ranges. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of specific resins as one resin are each within the above ranges.
  • any conventionally known method may be used (see, for example, the latest polyimide-basics and applications- (edited by the Japan Polyimide Study Group)).
  • a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then in the presence of an amine and a condensing agent.
  • a method for obtaining a resin containing a repeating unit represented by the formula (1) by a reaction with vinyl ethers or a reaction with a dialkyl acetal of dimethylformamide (synthesis method 1), and Makromol. Chem. , 194, 511 to 521 (1993), a method of synthesizing a dicarboxylic acid having an acid-degradable group and then polycondensing it with a diamine (synthesis method 2) is cost effective, easy to operate, and reproduces performance. It is preferable in terms of sex. (Synthesis method 1)
  • R 1 , R 2 and R 3 are synonymous with those in the formula (1).
  • the organic solvent that can be used in this polyamic acid synthesis reaction include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone.
  • Solvents aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, pyridine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples thereof include ether solvents such as tetrahydrofuran, dioxane, and digrim. Of these, an amide-based solvent is preferable, and a specific resin having a high molecular weight can be obtained.
  • the boiling point of the organic solvent used in the polymerization reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
  • the concentration of the solute in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.
  • the resin composition containing the specific resin is formed on a substrate such as a semiconductor substrate, and when the resin composition is photosensitive (when the formed film is a photosensitive film), it is subjected to the subsequent exposure step and development step.
  • a relief pattern can be formed. By the heat treatment of this pattern, dehydration ring closure of the specific resin occurs, and a polyimide cured product is obtained.
  • the film formed from the specific resin has an i-line transmittance of 1% or more, preferably 5% or more, and more preferably 10% or more per 20 ⁇ m film thickness. It is particularly preferably 10 to 80%. When this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern having a good shape with high resolution.
  • the transmittance of i-line (light having a wavelength of 365 nm) can be measured by a spectrophotometer (for example, Hitachi U3410 type, manufactured by Hitachi, Ltd.).
  • the residual stress of the polyimide cured product formed by imide ring closure from the polyamic acid ester having the repeating unit represented by the above formula (1) is preferably 35 MPa or less, more preferably 30 MPa or less. ..
  • the residual stress of the polyimide film can be measured at room temperature (25 ° C.) by a thin film stress measuring device (for example, FLX-2320 type manufactured by Tencor Co., Ltd.).
  • a resin having a repeating unit represented by the above formula (1) satisfying these characteristics is rigid and linear, for example, by selecting an appropriate raw material when synthesizing the resin, the aromatic ring ⁇ -conjugated length is suppressed. It will have a structure capable of forming a main chain.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more.
  • the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the specific resin may be used alone or in combination of two or more.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
  • Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
  • a (meth) acrylic resin a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
  • a high polymerizable base value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group contained in 1 g of the resin. (1 ⁇ 10 -3 mol / g or more)
  • a (meth) acrylic resin By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
  • the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred. Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the other resin may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention contains a photoacid generator.
  • the photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm.
  • the irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm.
  • the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
  • generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.
  • Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
  • Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.
  • quinone diazide compound a monovalent or polyvalent hydroxy compound with an ester bond of quinone diazide sulfonic acid, a monovalent or polyvalent amino compound with a sulfonate bond of quinone diazide sulfonic acid, and a polyhydroxypolyamino compound with quinone diazide.
  • examples thereof include those in which the sulfonic acid of the above is ester-bonded and / or sulfonic acid-bonded.
  • All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that 40 mol% or more of all the functional groups are substituted with quinonediazide on average. ..
  • a quinone diazide compound By containing such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray. ..
  • hydroxy compound phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, Tri
  • the amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4.
  • ′ -Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide and the like can be mentioned, but the present invention is not limited thereto.
  • polyhydroxypolyamino compound examples include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. ..
  • the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
  • the content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin. It is preferable to set the content of the quinonediazide compound in this range because the contrast between the exposed portion and the unexposed portion can be obtained and the sensitivity can be further increased. Further, a sensitizer or the like may be added as needed.
  • the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
  • the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
  • X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s exist, they may be the same or different from each other.
  • the alkyl group and the alkoxy group in X3 may have a substituent.
  • As the alkyl group in X3 a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.
  • As the alkoxy group in X3 a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.
  • halogen atom in X3 a chlorine atom or a fluorine atom is preferable.
  • m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3 , the plurality of X3s may be the same or different.
  • R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
  • W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms.
  • m3 is 3
  • X3 is a methyl group
  • X3 is substituted at the ortho position
  • R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,
  • a compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
  • oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
  • R s1 represents an alkyl group, an aryl group or a heteroaryl group
  • R s2, which may be present in a plurality of R s2 independently represents a hydrogen atom, an alkyl group and an aryl group
  • R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
  • Xs represents O or S.
  • ns represents 1 or 2
  • ms represents an integer from 0 to 6.
  • an alkyl group represented by R s1 preferably 1 to 30 carbon atoms
  • an aryl group preferably 6 to 30 carbon atoms
  • a heteroaryl group carbon
  • numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms).
  • Hydrogen atom or alkyl group is more preferable.
  • the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
  • Xs represents O or S, and is preferably O.
  • the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
  • the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
  • the alkyloxy group preferably having 1 to 30 carbon atoms
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
  • the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
  • the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
  • R t1 represents an alkyl group, an aryl group or a heteroaryl group
  • R t7 represents a hydrogen atom or a bromine atom
  • R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
  • R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
  • R t2 represents a hydrogen atom or a methyl group.
  • R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
  • R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group.
  • it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
  • R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
  • Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674.
  • the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
  • oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
  • Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group.
  • R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
  • Ru2a represents an alkyl group or an aryl group.
  • Xu is -O-, -S-, -NH-, -NR u5- , -CH 2- , -CR u6 H- or CR u6 R u7.
  • R u5 to R u7 independently represent an alkyl group or an aryl group, respectively.
  • Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group.
  • Two of R u1 to R u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a fused ring together with the benzene ring.
  • R u1 to Ru4 a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of Ru1 to Ru4 are bonded to each other to form an aryl group is also preferable. Above all, it is preferable that all of Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
  • the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
  • the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
  • Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
  • the following b-9, b-16, b-31, and b-33 are preferable.
  • Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like. Can be done.
  • organic halogenated compound examples include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
  • an oxazole compound substituted with a trihalomethyl group an S-triazine compound is given as a preferable example. More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)-.
  • Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710.
  • Japanese Patent Application Laid-Open No. 2000-131837 Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent Application Laid-Open No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98.
  • organic boron sulfonium complex or the organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561.
  • Specific examples thereof include organic boron transition metal coordination complexes such as JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Incorporated herein.
  • disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
  • onium salt compound examples include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, European Patents 104, 143, US Patents 339, 049, 410, 201, Japanese Patent Application Laid-Open No. Iodonium salt described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No.
  • onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
  • Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms.
  • Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable.
  • perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable.
  • Ar 21 and Ar 22 each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
  • Z21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
  • R 31 , R 32 , and R 33 each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability.
  • Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
  • Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms.
  • Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability.
  • perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
  • preferable photoacid generators include the following.
  • the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
  • the photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range. It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.
  • the resin composition of the present invention contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
  • esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
  • alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
  • cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
  • the resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance with time from exposure to heating.
  • the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa.
  • the acid trapping agent a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable.
  • the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned.
  • the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
  • Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
  • As an acid scavenger having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like.
  • Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
  • Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
  • Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like.
  • alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like.
  • aniline derivative having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline and the like.
  • preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N.
  • N-dimethylaniline diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N, N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin
  • the composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
  • the acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
  • the resin composition may contain a thermosetting accelerator.
  • the thermosetting accelerator include a thermal polymerization initiator, a thermal acid generator and the like.
  • a thermal polymerization initiator is included, and when the resin composition contains another cross-linking agent, a thermal acid generator is included.
  • thermal radical polymerization initiator As the thermal polymerization initiator, a thermal radical polymerization initiator may be particularly contained.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound.
  • Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
  • the resin composition may contain a thermal acid generator.
  • the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
  • the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
  • the thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
  • the acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
  • aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
  • alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
  • haloalkyl sulfonic acid such as sulfonic acid is preferable.
  • thermoacid generator include those described in paragraph 0055 of JP2013-072935.
  • alkyl sulfonic acid having 1 to 4 carbon atoms and haloalkyl sulfonic acid having 1 to 4 carbon atoms are generated. More preferably, methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, methanesulfonic acid.
  • Benzyl acid (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium , Trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) ) Methyl sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-((
  • JP2013-167742A is also preferable as the thermal acid generator.
  • the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin.
  • the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin.
  • the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the cured product (cured film) can be further improved.
  • 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound capable of generating a base by a physical or chemical action.
  • Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
  • the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator.
  • the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
  • the base generator may be an ionic base generator or a nonionic base generator.
  • Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator according to the present invention is not particularly limited, and a known base generator can be used.
  • Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides.
  • Compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, ⁇ -lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
  • Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
  • Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
  • Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
  • the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
  • the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
  • a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
  • Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
  • Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • substituents preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12
  • It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • cyclohexyl groups are more preferred.
  • Rb 3 examples include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18). ⁇ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable).
  • 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24).
  • 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
  • the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
  • Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
  • Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited.
  • Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
  • 2 to 8 are more preferable, 2 to 3 are more preferable
  • aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
  • Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms are preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
  • the compound represented by the formula (B1-1) is also preferable.
  • Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
  • Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more.
  • RN1 and RN2 each independently represent a monovalent organic group.
  • linking chain refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms).
  • L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length”) is 4.
  • the number of carbon atoms in L in the formula (B3) is preferably 3 to 24.
  • the upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
  • the lower limit is more preferably 4 or more.
  • the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable.
  • the chain length of L is preferably 4 or 5, and most preferably 4.
  • Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
  • the base generator contains a compound represented by the following formula (N1).
  • RN1 and RN2 each independently represent a monovalent organic group
  • RC1 represents a hydrogen atom or a protecting group
  • L represents a divalent linking group
  • L is a divalent linking group, preferably a divalent organic group.
  • the linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more.
  • the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
  • the linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.
  • RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred.
  • an aliphatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent.
  • an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
  • a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain.
  • Examples thereof include alkyl groups having.
  • the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
  • the linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group.
  • Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
  • the group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
  • the alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
  • the alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later.
  • a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
  • RN1 and RN2 may be connected to each other to form an annular structure.
  • oxygen atoms or the like may be contained in the chain.
  • the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
  • a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like.
  • Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.
  • RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
  • the protecting group a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
  • the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain.
  • the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like.
  • Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethimethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned.
  • MOM methyloxymethimethyl
  • EE ethyloxyethyl
  • Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
  • the divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable.
  • the hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group.
  • a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
  • the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
  • linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
  • a linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
  • the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
  • the group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
  • the alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
  • the alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
  • the linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
  • the cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
  • the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
  • a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
  • Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
  • the molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salt examples include, but are not limited to, the following compounds.
  • iminium salt examples include, but are not limited to, the following compounds.
  • the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
  • the lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
  • the base generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound include radical cross-linking agents and other cross-linking agents.
  • the resin composition of the present invention preferably contains a radical cross-linking agent.
  • the radical cross-linking agent is a compound having a radically polymerizable group.
  • a group containing an ethylenically unsaturated bond is preferable.
  • Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
  • a (meth) acryloyl group As the group containing the ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
  • the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical cross-linking agent may have three or more ethylenically unsaturated bonds.
  • As the compound having two or more ethylenically unsaturated bonds a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable.
  • the compound having is more preferable.
  • the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
  • the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
  • radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polymorphic acid group.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
  • Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof.
  • the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
  • Compounds having two or more groups and cardo resins can also be used.
  • the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
  • dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable.
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
  • TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
  • urethane oligomer UAS-10 are examples of the radical cross-linking agent.
  • UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
  • radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
  • the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • the radical cross-linking agent provided with the above is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
  • the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • the resin composition it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 dimethacrylate.
  • the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product).
  • Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used.
  • the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the bifunctional or higher functional cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.
  • the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
  • the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator.
  • a compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof.
  • a compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
  • the acid is preferably an acid generated from a photoacid generator in the exposure step.
  • a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group.
  • a compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
  • an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group.
  • examples thereof include compounds having a structure substituted with an alkoxymethyl group.
  • the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
  • the cross-linking agent using melamine is a melamine-based cross-linking agent
  • the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
  • the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
  • a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
  • the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom of the following urea structure, or on triazine.
  • the alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
  • the molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
  • Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
  • X represents a single-bonded or divalent organic group
  • each R 104 independently represents an alkyl group or an acyl group
  • R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • R 4 is independent, respectively, It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R5 represents a group desorbed by the action of an acid.
  • R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
  • R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ).
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be coupled to each other to form a ring.
  • an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • the alkyl group may be linear or branched.
  • cycloalkyl group a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
  • the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
  • aralkyl group an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
  • the above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • These groups are preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group and the like. More preferably, it is a tertiary alkyl ester group or an acetal ester group.
  • Examples of the compound having an alkoxymethyl group include the following structures.
  • Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
  • Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
  • melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
  • urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol.
  • Uril trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl
  • Glycol-based cross-linking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea and other urea-based cross-linking agents, monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea
  • benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
  • Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
  • the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
  • an aromatic ring preferably a benzene ring.
  • Compounds to which the group of the species is directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl.
  • suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
  • the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone.
  • n is an integer of 1 to 5
  • m is an integer of 1 to 20.
  • n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
  • oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like.
  • Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
  • benzoxazine compound examples include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo.
  • examples include oxazine compounds. These may be used alone or in combination of two or more.
  • the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
  • the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
  • the resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a ⁇ -ketoester. Examples thereof include compounds and amino compounds.
  • silane coupling agent examples include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992.
  • examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference.
  • silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
  • Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.
  • the resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
  • the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the resin composition of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
  • Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol
  • polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
  • the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
  • the resin composition of the present invention can be used with various additives such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, and oxidations, if necessary, to the extent that the effects of the present invention can be obtained.
  • Inhibitors, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries eg, antifoaming agents, flame retardant agents, etc.
  • properties such as film physical characteristics can be adjusted.
  • the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • surfactant various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
  • fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
  • F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
  • Florard FC430, FC431, FC171, Novek FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
  • Surfron S-382 SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.) ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.
  • the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein.
  • a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
  • silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
  • hydrocarbon-based surfactant examples include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anion-type surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
  • the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the resin composition of the present invention may contain inorganic fine particles.
  • specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
  • the average particle size of the fine particles is the primary particle size and the volume average particle size.
  • the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
  • the composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
  • salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
  • benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
  • Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
  • benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3).
  • Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
  • the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-
  • the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
  • the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
  • the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
  • Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
  • Specific examples of the organic titanium compound are shown in I) to VII) below:
  • I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained.
  • Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)).
  • Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
  • Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
  • Titanium oxide compound For example, titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
  • the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
  • -Pyrrole-1-yl) phenyl) titanium is preferred.
  • the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin.
  • the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
  • the composition of the present invention may contain an antioxidant.
  • an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
  • the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • a phosphorus-based antioxidant can also be preferably used.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
  • the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
  • the composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
  • Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification.
  • Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
  • preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
  • R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group.
  • R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom.
  • k represents an integer of 1 to 4.
  • the compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
  • metal oxidation can be suppressed by the rust preventive action on the metal material.
  • k is more preferably an integer of 2 to 4.
  • R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
  • R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
  • Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
  • alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion
  • -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
  • Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
  • the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin.
  • the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, photosensitive is exhibited.
  • the interaction with the agent improves the sensitivity of the resin composition.
  • Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present embodiment may contain an anti-aggregation agent, if necessary.
  • the antiaggregating agent include sodium polyacrylate and the like.
  • one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
  • the composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
  • the resin composition of the present embodiment may contain a phenolic compound, if necessary.
  • phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP.
  • one type of phenolic compound may be used alone, or two or more types may be used in combination.
  • the composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
  • Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof.
  • the other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
  • one type of other polymer compound may be used alone, or two or more types may be used in combination.
  • the composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
  • the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 3,000 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film.
  • the coating surface condition may deteriorate. ..
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
  • the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
  • the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention.
  • examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
  • the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • ion exchange treatment and the like are preferably mentioned.
  • a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
  • a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing contamination of raw materials and the resin composition of the present invention with impurities. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
  • the curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape.
  • the cured product is preferably in the form of a film.
  • this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape.
  • the film thickness of this cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
  • the developer of the present invention is a developer used in the method for producing a cured product of the present invention.
  • the developer of the present invention has the same meaning as the developer described in the developing step of the above-mentioned method for producing a cured product of the present invention, and the preferred embodiment is also the same.
  • the acetal form A-2 was synthesized in the same manner.
  • Chlor form B-2 was synthesized in the same manner.
  • the obtained diluted solution was cooled to -5 ° C or lower, and then 25.85 g (200 mmol) of diisopropylethylamine was added dropwise over 30 minutes, and then 2-methoxyethoxymethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 24. .91 g (200 mmol) was added dropwise over 1 hour and stirred at ⁇ 10 to ⁇ 5 ° C. for 1 hour.
  • the obtained stirred solution was added to 5 L of methanol, and the mixture was stirred for 30 minutes. After allowing the stirred solution to stand for 30 minutes, the supernatant was discarded to obtain a solid substance. After dissolving this solid in 300 mL of tetrahydrofuran, it was added to 5 L of hexane, stirred for 30 minutes, then filtered and dried to obtain 56 g of polymer P-1.
  • a solution prepared by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour.
  • 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours.
  • the mixed solution after stirring was added to 4 liters of water to precipitate the polyimide precursor resin, and then the mixture was stirred at a speed of 500 rpm for 15 minutes.
  • the obtained polyimide precursor resin was added to 4 liters of water, the mixture was stirred again for 30 minutes, and the mixture was filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain 33 g of P-2.
  • Examples and comparative examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Further, in the comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of the component described in the table is the amount described in the "Mass part" column of the table. Further, in each composition, the content of the solvent was adjusted so that the solid content concentration of the composition was the value (mass%) shown in the table.
  • the obtained resin composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter having a filter pore size of 0.8 ⁇ m. Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
  • ⁇ Silane coupling agent ⁇ -D-1 3-glycidoxypropylmethyldimethoxysilane-D-2: a compound having the following structure
  • ⁇ solvent ⁇ -GBL ⁇ -butyrolactone-DMSO: dimethyl sulfoxide
  • ratio the description in the "ratio" column indicates the content (% by mass) of each solvent with respect to the total mass of the solvent.
  • the exposure amount was 400 mJ / cm 2 .
  • a Toppan test chart No. 1, negative type, manufactured by Toppan Printing
  • the resin composition layer was heated for 300 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example in which "-" was described in the column of "PEB temperature (° C.)", heating was not performed. After the above heating, a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table. After the above development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
  • PGMEA propylene glycol monomethyl ether acetate
  • the pattern obtained after development was observed and evaluated according to the following evaluation criteria.
  • the evaluation results are described in the "Resolution" column in the table.
  • the resin composition layer was exposed to a stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) using a photomask in which a 1: 1 line-and-space pattern having a line width of 20 ⁇ m was formed. Was done. The exposure amount was 400 mJ / cm 2 .
  • the resin composition layer was heated for 5 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example in which "-" was described in the column of "PEB temperature (° C.)", heating was not performed. After the above heating, a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table.
  • the resin composition layer was exposed to a stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) using a photomask in which a 1: 1 line-and-space pattern having a line width of 20 ⁇ m was formed. Was done.
  • the exposed portion via the 1: 1 line and space pattern is set so that the line portion and the space portion are orthogonal to the exposed portion in the first layer.
  • the exposure amount was 400 mJ / cm 2 .
  • the resin composition layer was heated for 5 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example described as "-" in the column of "PEB temperature (° C.)", heating was not performed.
  • a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table. After the above development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate). The above pattern was heated at the temperature described in “cure temperature (° C.)” and the time described in “cure time (min)” in the table.
  • cure temperature ° C.
  • min time described in “cure time (min)” in the table.
  • N 2 oven in the column of "heating means”
  • heating was performed using CLH-21 manufactured by Koyo to obtain a cured product of the second layer.
  • heating was performed using RTP-6 manufactured by Advanced Riko Co., Ltd. to obtain a cured product of the second layer.
  • the taper angle is less than 80 °
  • the cross-sectional shape of the pattern is a reverse taper shape with a taper angle of more than 90 °, or the cross-sectional shape of the pattern is constricted, but the pattern is peeled off. I was not able to admit.
  • C Peeling of the pattern was observed.
  • the polyimide precursor does not have a group that causes a reaction in which the polarity is increased by the action of an acid, and so-called negative pattern formation is performed. In such an example, it can be seen that the resolution is inferior.
  • Example 101 The resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 300 seconds. The film thickness was set so that the film thickness of the obtained cured product was 5 ⁇ m. Then, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 120 ° C. for 300 seconds.
  • NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
  • Example 2 After the above heating, it was developed with the developer used in Example 1 and rinsed with the rinse solution used in Example 1 to obtain a layer pattern. Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the layer was cured by maintaining for 120 minutes to form an interlayer insulating film for the rewiring layer.
  • the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

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Abstract

The present invention provides: a method for manufacturing a cured product having superior resolution; a resin composition and developing solution used in the method for manufacturing a cured product; a method for manufacturing a layered body, said method including the method for manufacturing a cured product; and a method for manufacturing an electronic device, said method including the method for manufacturing a cured product or the method for manufacturing a layered body. The method for manufacturing a cured product includes: a film formation step using a resin composition that includes a resin, a compound that generates an acid by exposure, and a solvent; an exposure step; a developing step; and a modifying step, the resin being a polyimide precursor and having a group that generates a reaction in which polarity is increased due to the effect of the acid, the content of an organic solvent in the developing solution being 80 mass% or more, and the solubility of the pattern in the solvent included in the resin composition being reduced by the modification.

Description

硬化物の製造方法、樹脂組成物、現像液、積層体の製造方法、及び、半導体デバイスの製造方法A method for manufacturing a cured product, a resin composition, a developing solution, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device.
　本発明は、硬化物の製造方法、樹脂組成物、現像液、積層体の製造方法、及び、半導体デバイスの製造方法に関する。 The present invention relates to a method for producing a cured product, a resin composition, a developer, a method for producing a laminate, and a method for producing a semiconductor device.
　ポリイミド等の樹脂は、耐熱性及び絶縁性等に優れるため、様々な用途に適用されている。上記用途としては特に限定されないが、実装用の半導体デバイスを例に挙げると、これらの樹脂を含むパターンを、絶縁膜や封止材の材料、又は、保護膜として利用すること等が挙げられる。また、これらの樹脂を含むパターンは、フレキシブル基板のベースフィルムやカバーレイなどとしても用いられている。 Resins such as polyimide are applied to various applications because they have excellent heat resistance and insulating properties. The application is not particularly limited, and examples thereof include semiconductor devices for mounting, such as using a pattern containing these resins as a material for an insulating film or a sealing material, or as a protective film. In addition, patterns containing these resins are also used as base films and coverlays for flexible substrates.
　例えば上述した用途において、ポリイミド等の樹脂は、ポリイミド前駆体を含む樹脂組成物の形態で用いられる。
　このような樹脂組成物を、例えば塗布等により基材上に適用し、その後、必要に応じて露光、現像、変性等を行うことにより、ポリイミド前駆体の硬化物を基材上に形成することができる。
　樹脂組成物は、公知の塗布方法等により適用可能であり、現像により微細なパターン、複雑な形状のパターン等を形成できるため、硬化膜の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミド等が有する高い性能に加え、このような製造上の適応性に優れる観点から、ポリイミド前駆体を含む樹脂組成物を用いた硬化物の製造方法について、産業上の応用展開がますます期待されている。 For example, in the above-mentioned applications, a resin such as polyimide is used in the form of a resin composition containing a polyimide precursor.
A cured product of a polyimide precursor is formed on a substrate by applying such a resin composition onto a substrate by, for example, coating, and then subjecting it to exposure, development, modification, etc., if necessary. Can be done.
The resin composition can be applied by a known coating method or the like, and a fine pattern, a pattern having a complicated shape, or the like can be formed by development. It can be said that it is excellent. In addition to the high performance of polyimide and the like, from the viewpoint of excellent manufacturing adaptability, industrial application development is expected for a method for manufacturing a cured product using a resin composition containing a polyimide precursor. ing.
　例えば、特許文献１には、ネガ型感光性樹脂組成物を用いて塗膜又は成形体を形成し、上記塗膜又は成形体に所定パターン状に電磁波を照射後、未露光部の塗膜を除去してパターンを形成する現像工程の前に、上記塗膜又は成形体を加熱する工程を有するレリーフパターンの製造方法であって、上記加熱する工程が、系外から積極的かつ継続的に気体が供給され、且つ、上記塗膜又は成形体から発生する揮発性成分が系外に積極的に除去される雰囲気下で、熱媒体を介するか、電磁波の輻射により、上記塗膜又は成形体を加熱する工程であることを特徴とする、レリーフパターンの製造方法が記載されている。 For example, in Patent Document 1, a coating film or a molded product is formed using a negative photosensitive resin composition, the coating film or the molded product is irradiated with an electromagnetic wave in a predetermined pattern, and then the coating film on an unexposed portion is applied. A method for producing a relief pattern, which comprises a step of heating the coating film or a molded product before the developing step of removing and forming a pattern, wherein the heating step is a positive and continuous gas from outside the system. In an atmosphere in which volatile components generated from the coating film or the molded product are positively removed from the system, the coating film or the molded product is subjected to the heat medium or by the radiation of electromagnetic waves. A method for producing a relief pattern, which is a step of heating, is described.
特開２０１１－２２７４８５号公報Japanese Unexamined Patent Publication No. 2011-227485
　従来の硬化物の製造方法において、解像性を向上することが求められている。 In the conventional method for producing a cured product, it is required to improve the resolution.
　本発明は、解像性に優れた硬化物の製造方法、上記硬化物の製造方法に用いられる樹脂組成物、上記硬化物の製造方法に用いられる現像液、上記硬化物の製造方法を含む積層体の製造方法、及び、上記硬化物の製造方法又は上記積層体の製造方法を含む電子デバイスの製造方法を提供することを目的とする。 The present invention includes a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developing solution used in the method for producing the cured product, and a lamination method including the method for producing the cured product. It is an object of the present invention to provide a method for manufacturing a body, and a method for manufacturing an electronic device including the method for manufacturing the cured product or the method for manufacturing the laminate.
　本発明の代表的な実施態様の例を以下に示す。
＜１＞　樹脂、活性光線又は放射線の照射により酸を発生する化合物、及び、溶剤を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、
　上記膜を選択的に露光する露光工程、
　上記露光後の膜を現像液を用いて現像してパターンを形成する現像工程、並びに、
　上記パターンを変性させる変性工程を含み、
　上記樹脂がポリイミド前駆体であり、
　上記樹脂は酸の作用により極性が増大する反応を生じる基を有し、
　上記現像液の全質量に対する有機溶剤の含有量が８０質量％以上であり、
　上記変性により、上記樹脂組成物が含む溶剤に対して上記パターンの溶解性が低下する、
　硬化物の製造方法。
＜２＞　得られる硬化物の膜厚が５μｍ以上である、＜１＞に記載の硬化物の製造方法。＜３＞　上記樹脂が下記式（１）で表される繰返し単位を含む、＜１＞又は＜２＞に記載の硬化物の製造方法。
Figure JPOXMLDOC01-appb-C000003
 　上記式（１）中、Ｒ１は、４価の有機基を表す；複数のＲ１は互いに同一であっても異なっていてもよい；Ｒ２は、２価の有機基を表す；複数のＲ２は互いに同一であっても異なっていてもよい；Ｒ３は、各々独立に、水素原子又は有機基を表す。
＜４＞　上記式（１）で表される繰り返し単位が上記酸の作用により極性が増大する反応を生じる基を有する、＜３＞に記載の硬化物の製造方法。
＜５＞　上記樹脂組成物が酸捕捉剤を更に含む、＜１＞～＜４＞のいずれか１つに記載の硬化物の製造方法。
＜６＞　上記現像液が、ハンセン溶解度パラメータの水素結合項ｄＨの値が８以下である有機溶剤を８０質量％以上含む、＜１＞～＜５＞のいずれか１つに記載の硬化物の製造方法。
＜７＞　上記酸の作用により極性が増大する反応を生じる基が下記式（Ａ－１）又は下記式（Ａ－２）で表される基である、＜１＞～＜６＞のいずれか１つに記載の硬化物の製造方法。
Figure JPOXMLDOC01-appb-C000004
 　式（Ａ－１）中、ＲＡ１～ＲＡ５はそれぞれ独立に、水素原子又は１価の有機基を表し、ＲＡ１～ＲＡ５のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す；
　式（Ａ－２）中、ＲＡ６～ＲＡ８はそれぞれ独立に、１価の有機基を表し、ＲＡ６～ＲＡ８のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す。
＜８＞　上記変性工程において、上記パターンの加熱が行われる、＜１＞～＜７＞のいずれか１つに記載の硬化物の製造方法。
＜９＞　上記露光工程後、上記現像工程前に、上記膜を加熱する工程を更に含む、＜１＞～＜８＞のいずれか１つに記載の硬化物の製造方法。
＜１０＞　＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法を複数回繰り返すことを含む
　積層体の製造方法。
＜１１＞　複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含む、＜１０＞に記載の積層体の製造方法。
＜１２＞　＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法、又は、＜１０＞若しくは＜１１＞に記載の積層体の製造方法を含む、
　電子デバイスの製造方法。
＜１３＞　＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法に用いられる樹脂組成物。
＜１４＞　＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法に用いられる現像液。 Examples of typical embodiments of the present invention are shown below.
<1> A film forming step of applying a resin, a compound that generates an acid by irradiation with active light or radiation, and a resin composition containing a solvent onto a substrate to form a film.
An exposure process that selectively exposes the film,
A developing step of developing the exposed film with a developing solution to form a pattern, and
Including a modification step of modifying the above pattern,
The above resin is a polyimide precursor,
The above resin has a group that causes a reaction in which the polarity is increased by the action of an acid.
The content of the organic solvent with respect to the total mass of the developer is 80% by mass or more, and the content is 80% by mass or more.
The modification reduces the solubility of the pattern in the solvent contained in the resin composition.
A method for manufacturing a cured product.
<2> The method for producing a cured product according to <1>, wherein the obtained cured product has a film thickness of 5 μm or more. <3> The method for producing a cured product according to <1> or <2>, wherein the resin contains a repeating unit represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 In formula (1) above, R 1 represents a tetravalent organic group; a plurality of R 1s may be the same or different from each other; R 2 represents a divalent organic group; R 2 may be the same as or different from each other; R 3 each independently represents a hydrogen atom or an organic group.
<4> The method for producing a cured product according to <3>, wherein the repeating unit represented by the above formula (1) has a group that causes a reaction in which the polarity is increased by the action of the above acid.
<5> The method for producing a cured product according to any one of <1> to <4>, wherein the resin composition further contains an acid scavenger.
<6> The cured product according to any one of <1> to <5>, wherein the developer contains 80% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameter of 8 or less. Production method.
<7> Any of <1> to <6>, wherein the group that causes a reaction in which the polarity is increased by the action of the above acid is a group represented by the following formula (A-1) or the following formula (A-2). The method for producing a cured product according to one.
Figure JPOXMLDOC01-appb-C000004
 In the formula (A-1), RA1 to RA5 each independently represent a hydrogen atom or a monovalent organic group, and even if at least two of RA1 to RA5 are bonded to form a ring structure. Often, * represents the binding site with other structures;
In the formula (A-2), RA6 to RA8 each independently represent a monovalent organic group, and at least two of RA6 to RA8 may be bonded to form a ring structure *. Represents a binding site with another structure.
<8> The method for producing a cured product according to any one of <1> to <7>, wherein the heating of the pattern is performed in the modification step.
<9> The method for producing a cured product according to any one of <1> to <8>, further comprising a step of heating the film after the exposure step and before the development step.
<10> A method for producing a laminated body, which comprises repeating the method for producing a cured product according to any one of <1> to <9> a plurality of times.
<11> The method for producing a laminate according to <10>, further comprising a metal layer forming step of forming a metal layer on a layer made of the cured product during a method for producing a cured product which is performed a plurality of times.
<12> The method for producing a cured product according to any one of <1> to <9>, or the method for producing a laminate according to <10> or <11>.
How to manufacture electronic devices.
<13> The resin composition used in the method for producing a cured product according to any one of <1> to <9>.
<14> The developer used in the method for producing a cured product according to any one of <1> to <9>.
　本発明によれば、解像性に優れた硬化物の製造方法、上記硬化物の製造方法に用いられる樹脂組成物、上記硬化物の製造方法に用いられる現像液、上記硬化物の製造方法を含む積層体の製造方法、及び、上記硬化物の製造方法又は上記積層体の製造方法を含む電子デバイスの製造方法が提供される。 According to the present invention, a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developing solution used in the method for producing the cured product, and a method for producing the cured product are used. Provided are a method for producing a laminate including the above, and a method for producing the cured product or a method for producing an electronic device including the method for producing the laminate.
　以下、本発明の主要な実施形態について説明する。しかしながら、本発明は、明示した実施形態に限られるものではない。
　本明細書において「～」という記号を用いて表される数値範囲は、「～」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
　本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有しない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線又は放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「（メタ）アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「（メタ）アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
　本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ）法を用いて測定した値であり、ポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０ＧＰＣ（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、及び、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（以上、東ソー（株）製）を直列に連結して用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。ただし、溶解性が低い場合など、溶離液としてＴＨＦが適していない場合にはＮＭＰ（Ｎ－メチル－２－ピロリドン）を用いることもできる。また、ＧＰＣ測定における検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。
　本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第３の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、樹脂組成物層がある場合には、基材から樹脂組成物層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
　本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する２種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
　本明細書において、特に述べない限り、温度は２３℃、気圧は１０１，３２５Ｐａ（１気圧）、相対湿度は５０％ＲＨである。
　本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series. Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as the eluent, such as when the solubility is low. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atmospheric pressure), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.
（硬化物の製造方法）
　本発明の硬化物の製造方法は、樹脂、活性光線又は放射線の照射により酸を発生する化合物（以下、「光酸発生剤」ともいう。）、及び、溶剤を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、上記膜を活性光線又は放射線を用いてパターン露光する露光工程、現像液により、上記露光後の膜を現像してパターンを得る現像工程、並びに、上記パターンを変性させる変性工程を含み、上記樹脂がポリイミド前駆体であり、上記樹脂は酸の作用により極性が増大する反応を生じる基（以下、「極性変換基」ともいう。）を有し、上記現像液の全質量に対する有機溶剤の含有量が８０質量％以上であり、上記変性により、上記樹脂組成物が含む溶剤に対して上記パターンの溶解性が低下する、硬化物の製造方法である。
　以下、本発明において、ポリイミド前駆体であり、極性変換基を有する樹脂を、「特定樹脂」ともいう。
　本発明の硬化物の製造方法によれば、解像性に優れた硬化物が得られる。
　上記効果が得られるメカニズムは不明であるが、下記のように推測される。 (Manufacturing method of cured product)
In the method for producing a cured product of the present invention, a resin, a compound that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as "photoacid generator"), and a resin composition containing a solvent are placed on a substrate. A film forming step of forming a film by applying to the above, an exposure step of exposing the film to a pattern using active light or radiation, a developing step of developing the exposed film with a developing solution to obtain a pattern, and the above. The above-mentioned resin includes a modification step of modifying a pattern, and the above-mentioned resin is a polyimide precursor, and the above-mentioned resin has a group (hereinafter, also referred to as “polarity conversion group”) that causes a reaction in which the polarity is increased by the action of an acid. This is a method for producing a cured product, wherein the content of the organic solvent with respect to the total mass of the developing solution is 80% by mass or more, and the solubility of the pattern in the solvent contained in the resin composition is lowered by the modification.
Hereinafter, in the present invention, a resin that is a polyimide precursor and has a polarity converting group is also referred to as a “specific resin”.
According to the method for producing a cured product of the present invention, a cured product having excellent resolution can be obtained.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
　極性変換基を有するポリイミド前駆体及び光酸発生剤を含む樹脂組成物から形成された膜を用い、かつ、有機溶剤の含有量が８０質量％以上である現像液を用いることにより、ネガ型パターンを形成することができる。
　ネガ型パターンとは、現像工程において膜の未露光部が除去されたパターンをいう。
　具体的には、露光工程において、露光部では光酸発生剤から酸が発生し、上記酸の作用により樹脂の極性変換基における極性が増大するため、露光部においては上記樹脂の上記現像液に対する溶解性が低下して、現像工程後には露光部が残存し、未露光部が除去される。
　ここで、上記極性の増大により、露光部に対する現像液の侵入が抑制されるため、得られるパターンの現像液による膨潤が抑制されると考えられる。
　上記膨潤の抑制により、例えばホールパターンを形成する場合、微細なホールパターンにおいても開口したホールパターンが得られやすいと考えられる。
　また、上記膨潤の抑制により、例えばラインパターンを形成する場合、ライン部の膨潤が抑制され、より微細なラインパターンが形成しやすいと考えられる。
　すなわち、本発明の硬化物の製造方法によれば、微細なパターンを形成することができ、解像性に優れるといえる。
　さらに、本発明の組成物は変性により樹脂組成物に含まれる溶剤への溶解性が低下するため、得られるパターン上に更に別の樹脂組成物を適用して積層構造とした場合においても、パターンが樹脂組成物に溶解しにくく、積層時の１層目のパターンの寸法安定性に優れ、また、積層時の２層目のパターンの解像性に優れるなど、積層パターンの形成性にも優れると推測される。 Negative pattern by using a film formed from a resin composition containing a polyimide precursor having a polarity converting group and a photoacid generator, and by using a developer having an organic solvent content of 80% by mass or more. Can be formed.
The negative pattern is a pattern in which the unexposed portion of the film is removed in the developing process.
Specifically, in the exposure step, an acid is generated from the photoacid generator in the exposed part, and the polarity of the polarity converting group of the resin is increased by the action of the acid. The solubility is reduced, the exposed portion remains after the developing step, and the unexposed portion is removed.
Here, it is considered that the increase in the polarity suppresses the intrusion of the developer into the exposed portion, so that the swelling of the obtained pattern due to the developer is suppressed.
By suppressing the swelling, for example, when a hole pattern is formed, it is considered that an open hole pattern can be easily obtained even in a fine hole pattern.
Further, it is considered that, for example, when a line pattern is formed by suppressing the swelling, the swelling of the line portion is suppressed and a finer line pattern is likely to be formed.
That is, according to the method for producing a cured product of the present invention, it can be said that a fine pattern can be formed and the resolution is excellent.
Further, since the composition of the present invention is modified to reduce the solubility in the solvent contained in the resin composition, even when another resin composition is applied on the obtained pattern to form a laminated structure, the pattern is formed. Is difficult to dissolve in the resin composition, has excellent dimensional stability of the pattern of the first layer during lamination, and has excellent resolution of the pattern of the second layer during lamination, and is also excellent in formability of the laminated pattern. It is presumed.
　ここで、特許文献１には、極性変換基を有するポリイミド前駆体及び光酸発生剤を含む樹脂組成物から形成された膜を用い、かつ、有機溶剤の含有量が８０質量％以上である現像液を用いることについては記載されていない。
　以下、本発明の硬化物の製造方法について詳細に説明する。 Here, in Patent Document 1, a film formed from a resin composition containing a polyimide precursor having a polarity converting group and a photoacid generator is used, and the content of an organic solvent is 80% by mass or more. There is no mention of using liquid.
Hereinafter, the method for producing a cured product of the present invention will be described in detail.
＜膜形成工程＞
　本発明の硬化物の製造方法は、樹脂、活性光線又は放射線の照射により酸を発生する化合物、及び、溶剤を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む。
　本発明において用いられる樹脂組成物の詳細については後述する。 <Membrane formation process>
The method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a resin, a compound that generates an acid by irradiation with active light or radiation, and a solvent onto a substrate to form a film. ..
Details of the resin composition used in the present invention will be described later.
〔基材〕
　基材の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基材、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基材（例えば、金属から形成された基材、及び、金属層が例えばめっきや蒸着等により形成された基材のいずれであってもよい）、紙、ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）、ＴＦＴ（薄膜トランジスタ）アレイ基材、モールド基材、プラズマディスプレイパネル（ＰＤＰ）の電極板などが挙げられ、特に制約されない。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Ｃｕ基材およびモールド基材がより好ましい。
　また、これらの基材にはヘキサメチルジシラザン（ＨＭＤＳ）等による密着層や酸化層などの層が表面に設けられていてもよい。
　また、基材の形状は特に限定されず、円形状であってもよく、矩形状であってもよい。
　基材のサイズとしては、円形状であれば、例えば直径が１００～４５０ｍｍであり、好ましくは２００～４５０ｍｍである。矩形状であれば、例えば短辺の長さが１００～１０００ｍｍであり、好ましくは２００～７００ｍｍである。
　また、基材としては、例えば板状、好ましくはパネル状の基材（基板）が用いられる。 〔Base material〕
The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used.
　また、樹脂層（例えば、硬化物からなる層）の表面や金属層の表面に樹脂組成物を適用して膜を形成する場合は、樹脂層や金属層が基材となる。 Further, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
　本発明の樹脂組成物を基材上に適用する手段としては、塗布が好ましい。 Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
　適用する手段としては、具体的には、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、インクジェット法などが例示される。膜の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、又は、インクジェット法であり、膜の厚さの均一性の観点および生産性の観点からスピンコート法およびスリットコート法が好ましい。方法に応じて樹脂組成物の固形分濃度や塗布条件を調整することで、所望の厚さの膜を得ることができる。また、基材の形状によっても塗布方法を適宜選択でき、ウエハ等の円形基材であればスピンコート法、スプレーコート法、インクジェット法等が好ましく、矩形基材であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、５００～３，５００ｒｐｍの回転数で、１０秒～３分程度適用することができる。
　また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
　転写方法に関しては特開２００６－０２３６９６号公報の段落００２３、００３６～００５１や、特開２００６－０４７５９２号公報の段落００９６～０１０８に記載の作製方法を本発明においても好適に用いることができる。
　また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス（ＥＢＲ）、バックリンスなどが挙げられる。
　また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity. The method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
＜乾燥工程＞
　上記膜は、膜形成工程（層形成工程）の後に、溶剤を除去するために、形成された膜（層）を乾燥する工程(乾燥工程)に供されてもよい。
　すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を乾燥する乾燥工程を含んでもよい。
　また、上記乾燥工程は膜形成工程の後、露光工程の前に行われることが好ましい。
　乾燥工程における膜の乾燥温度は５０～１５０℃であることが好ましく、７０℃～１３０℃がより好ましく、９０℃～１１０℃が更に好ましい。また、減圧により乾燥を行っても良い。乾燥時間としては、３０秒～２０分が例示され、１分～１０分が好ましく、２分～７分がより好ましい。 <Drying process>
The film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent after the film forming step (layer forming step).
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.
Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
＜露光工程＞
　上記膜は、膜を選択的に露光する露光工程に供される。
　すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を選択的に露光する露光工程を含む。
　選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域（露光部）と露光されていない領域（非露光部）が形成される。
　露光量は、本発明の樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長３６５ｎｍでの露光エネルギー換算で５０～１０，０００ｍＪ／ｃｍ２が好ましく、２００～８，０００ｍＪ／ｃｍ２がより好ましい。 <Exposure process>
The film is subjected to an exposure step of selectively exposing the film.
That is, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed by the film forming step.
Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
　露光波長は、１９０～１，０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。 The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
　露光波長は、光源との関係でいうと、（１）半導体レーザー（波長　８３０ｎｍ、５３２ｎｍ、４８８ｎｍ、４０５ｎｍ、３７５ｎｍ、３５５ｎｍ　ｅｔｃ．）、（２）メタルハライドランプ、（３）高圧水銀灯、ｇ線（波長　４３６ｎｍ）、ｈ線（波長　４０５ｎｍ）、ｉ線（波長　３６５ｎｍ）、ブロード（ｇ，ｈ，ｉ線の３波長）、（４）エキシマレーザー、ＫｒＦエキシマレーザー（波長　２４８ｎｍ）、ＡｒＦエキシマレーザー（波長　１９３ｎｍ）、Ｆ２エキシマレーザー（波長　１５７ｎｍ）、（５）極端紫外線；ＥＵＶ（波長　１３．６ｎｍ）、（６）電子線、（７）ＹＡＧレーザーの第二高調波５３２ｎｍ、第三高調波３５５ｎｍ等が挙げられる。本発明の樹脂組成物については、特に高圧水銀灯による露光が好ましく、中でも、ｉ線による露光が好ましい。これにより、特に高い露光感度が得られうる。
　また、露光の方式は特に限定されず、本発明の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。 The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength). 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. Will be. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
The exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
＜露光後加熱工程＞
　上記膜は、露光後に加熱する工程（露光後加熱工程）に供されてもよい。
　すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
　露光後加熱工程は、露光工程後、現像工程前に行うことができる。
　露光後加熱工程における加熱温度は、５０℃～１４０℃であることが好ましく、６０℃～１２０℃であることがより好ましい。
　露光後加熱工程における加熱時間は、３０秒間～３００分間が好ましく、１分間～１０分間がより好ましい。
　露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで１～１２℃／分が好ましく、２～１０℃／分がより好ましく、３～１０℃／分が更に好ましい。
　また、昇温速度は加熱途中で適宜変更してもよい。
　また、所望の温度に設定済みのホットプレートやオーブン等で加熱を行なう態様も好ましい。
　露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
　また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。 <Heating process after exposure>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
The post-exposure heating step can be performed after the exposure step and before the developing step.
The heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature.
Further, the heating rate may be appropriately changed during heating.
Further, it is also preferable to heat the product in a hot plate, an oven, or the like that has been set to a desired temperature.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
＜現像工程＞
　露光後の上記膜は、現像液を用いて現像してパターンを形成する現像工程に供される。
　すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含む。
　現像を行うことにより、膜の非露光部が除去され、パターンが形成される。
　ここで、膜の非露光部が現像工程により除去される現像をネガ型現像といい、膜の露光部が現像工程により除去される現像をポジ型現像という。 <Development process>
The film after exposure is subjected to a developing step of developing with a developing solution to form a pattern.
That is, the method for producing a cured product of the present invention includes a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern.
By developing, the unexposed portion of the film is removed and a pattern is formed.
Here, the development in which the non-exposed portion of the film is removed by the developing step is called negative type development, and the development in which the exposed portion of the film is removed by the developing step is called positive type development.
〔現像液〕
　本発明の硬化膜の製造方法において用いられる現像液は、現像液の全質量に対する有機溶剤の含有量が８０質量％以上である。 [Developer]
The developer used in the method for producing a cured film of the present invention has an organic solvent content of 80% by mass or more with respect to the total mass of the developer.
－有機溶剤－
　現像液は、現像液の全質量に対して有機溶剤を９０質量％以上含むことが好ましく、９５質量％以上含むことがより好ましく、９８質量％以上含むことが更に好ましい。上記有機溶剤の含有量の上限は、特に限定されず、１００質量％であってもよい。
　また、現像液は、ハンセン溶解度パラメータの水素結合項ｄＨの値が８以下である有機溶剤を８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、９５質量％以上含むことが更に好ましく、９８質量％以上含むことが特に好ましい。上記ｄＨの値が８以下である有機溶剤の含有量の上限は、特に限定されず、１００質量％であってもよい。
　有機溶剤におけるハンセン溶解度パラメータの水素結合項ｄＨは、ハンセン溶解度パラメータソフトウェア（ＨＳＰｉＰ）を用いて算出される値である。 -Organic solvent-
The developing solution preferably contains 90% by mass or more of an organic solvent, more preferably 95% by mass or more, and further preferably 98% by mass or more, based on the total mass of the developing solution. The upper limit of the content of the organic solvent is not particularly limited and may be 100% by mass.
Further, the developer preferably contains 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameter of 8 or less. It is more preferable, and it is particularly preferable to contain 98% by mass or more. The upper limit of the content of the organic solvent having a dH value of 8 or less is not particularly limited and may be 100% by mass.
The hydrogen bond term dH of the Hansen solubility parameter in an organic solvent is a value calculated using the Hansen solubility parameter software (HSPiP).
　有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類、スルホキシド類としてジメチルスルホキシド、並びに、アルコール類として、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、オクタノール、ジエチレングリコール、プロピレングリコール、メチルイソブチルカルビノール、トリエチレングリコール等、並びに、アミド類として、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、ジメチルホルムアミド等が好適に挙げられる。 Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono Procionate Luacetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, toluene, xylene. , Aromatic hydrocarbons such as anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol as alcohols. Methylisobutylcarbinol, triethylene glycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
　現像液が有機溶剤を含む場合、有機溶剤は１種又は、２種以上を混合して使用することができる。本発明では特にシクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン、及び、シクロヘキサノンよりなる群から選ばれた少なくとも１種を含む現像液が好ましく、シクロペンタノン、γ－ブチロラクトン及びジメチルスルホキシドよりなる群から選ばれた少なくとも１種を含む現像液がより好ましく、シクロペンタノンを含む現像液が最も好ましい。 When the developer contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and γ-butyrolactone are preferable. A developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
　現像液は、他の成分を更に含んでもよい。
　他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
〔現像液の供給方法〕
　現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、膜が形成された基材を現像液に浸漬する方法、基材上に形成された膜にノズルを用いて現像液を供給するパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
　現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
　また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
　また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
The method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle. There is a method of paddle development or a method of continuously supplying a developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
　現像時間としては、１０秒～１０分間が好ましく、２０秒～５分間がより好ましい。現像時の現像液の温度は、特に定めるものではないが、好ましくは、１０～４５℃、より好ましくは、１８℃～３０℃で行うことができる。 The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
　現像工程において、現像液を用いた処理の後、更に、リンス液によるパターンの洗浄（リンス）を行ってもよい。また、パターン上に接する現像液が乾燥しきらないうちにリンス液を供給するなどの方法を採用しても良い。 In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
〔リンス液〕
　現像液がアルカリ水溶液である場合、リンス液としては、例えば水を用いることができる。現像液が有機溶剤を含む現像液である場合、リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤（例えば、水、現像液に含まれる有機溶剤とは異なる有機溶剤）を用いることができる。 [Rinse liquid]
When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
　リンス液が有機溶剤を含む場合の有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類、スルホキシド類としてジメチルスルホキシド、並びに、アルコール類として、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、オクタノール、ジエチレングリコール、プロピレングリコール、メチルイソブチルカルビノール、トリエチレングリコール等、並びに、アミド類として、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、ジメチルホルムアミド等が好適に挙げられる。 When the rinsing solution contains an organic solvent, the esters include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl acid acid, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran. , Ethyl Glycol Monomethyl Ether, Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example. , Aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols. , Propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
　リンス液が有機溶剤を含む場合、有機溶剤は１種又は、２種以上を混合して使用することができる。本発明では特にシクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、Ｎ－メチルピロリドン、シクロヘキサノン、ＰＧＭＥＡ、ＰＧＭＥが好ましく、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、ＰＧＭＥＡ、ＰＧＭＥがより好ましく、シクロヘキサノン、ＰＧＭＥＡがさらに好ましい。 When the rinsing liquid contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.
　リンス液が有機溶剤を含む場合、リンス液は、５０質量％以上が有機溶剤であることが好ましく、７０質量％以上が有機溶剤であることがより好ましく、９０質量％以上が有機溶剤であることが更に好ましい。また、リンス液は、１００質量％が有機溶剤であってもよい。 When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.
　リンス液は、他の成分を更に含んでもよい。
　他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
〔リンス液の供給方法〕
　リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドル現像、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段により現像液を連続供給する方法がある。
　リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
　すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
　またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the paddle development on the base material, the method of supplying the rinsing liquid to the base material with a shower, and the base material. There is a method of continuously supplying the developer by means such as a straight nozzle on the top.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sonic or the like and a process of combining them can be adopted.
　リンス時間としては、１０秒～１０分間が好ましく、２０秒～５分間がより好ましい。リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、１０～４５℃、より好ましくは、１８℃～３０℃で行うことができる。 The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
＜変性工程＞
　本発明の硬化物の製造方法は、上記パターン（現像工程により得られたパターン）を変性させる変性工程を含む。
　変性工程は、上記パターン内で上記ポリイミド前駆体のイミド化を行う工程であることが好ましい。
　また、変性工程において、上記パターンの加熱が行われることが好ましい。
　すなわち、変性工程は、加熱により上記パターン内で上記ポリイミド前駆体のイミド化を行う工程であることが好ましい。
　加熱は、下記加熱工程に記載の方法により行うことが好ましい。 <Denaturation process>
The method for producing a cured product of the present invention includes a modification step of modifying the above pattern (pattern obtained by the development step).
The modification step is preferably a step of imidizing the polyimide precursor in the pattern.
Further, it is preferable that the heating of the above pattern is performed in the modification step.
That is, the modification step is preferably a step of imidizing the polyimide precursor in the pattern by heating.
The heating is preferably performed by the method described in the heating step below.
＜加熱工程＞
　現像工程により得られたパターン（リンス工程を行う場合は、リンス後のパターン）は、上記現像により得られたパターンを加熱する加熱工程に供されてもよい。
　すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含んでもよい。
　また、本発明の硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、膜形成工程により得られた膜を加熱する加熱工程を含んでもよい。
　加熱工程において、ポリイミド前駆体等の樹脂は環化してポリイミド等の樹脂となる。
　また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
　加熱工程における加熱温度（最高加熱温度）としては、５０～４５０℃が好ましく、１５０～３５０℃がより好ましく、１５０～２５０℃が更に好ましく、１６０～２５０℃が一層好ましく、１６０～２３０℃が特に好ましい。 <Heating process>
The pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
In addition, cross-linking of unreacted cross-linking groups with a specific resin or a cross-linking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
　加熱工程における加熱は、加熱開始時の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましい。上記昇温速度は２～１０℃／分がより好ましく、３～１０℃／分が更に好ましい。昇温速度を１℃／分以上とすることにより、生産性を確保しつつ、酸又は溶剤の過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化物の残存応力を緩和することができる。
　加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで１～８℃／秒の昇温速度で行うことが好ましく、２～７℃／秒がより好ましく、３～６℃／秒が更に好ましい。 The heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, curing is possible. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.
　加熱開始時の温度は、２０℃～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃が更に好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、本発明の樹脂組成物を基材の上に適用した後、乾燥させる場合、この乾燥後の膜（層）の温度であり、例えば、本発明の樹脂組成物に含まれる溶剤の沸点よりも、３０～２００℃低い温度から昇温させることが好ましい。 The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention. However, it is preferable to raise the temperature from a temperature as low as 30 to 200 ° C.
　加熱時間（最高加熱温度での加熱時間）は、５～３６０分であることが好ましく、１０～３００分であることがより好ましく、１５～２４０分であることが更に好ましい。 The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
　特に多層の積層体を形成する場合、層間の密着性の観点から、加熱温度は３０℃以上であることが好ましく、８０℃以上であることがより好ましく、１００℃以上であることが更に好ましく、１２０℃以上であることが特に好ましい。
　上記加熱温度の上限は、３５０℃以下であることが好ましく、２５０℃以下であることがより好ましく、２４０℃以下であることが更に好ましい。 In particular, when forming a multi-layered laminate, the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
The upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.
　加熱は段階的に行ってもよい。例として、２５℃から１２０℃まで３℃／分で昇温し、１２０℃にて６０分保持し、１２０℃から１８０℃まで２℃／分で昇温し、１８０℃にて１２０分保持する、といった工程を行ってもよい。また、米国特許第９１５９５４７号明細書に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うとよく、１５秒～３０分間がより好ましい。前処理は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で１段階目の前処理工程を行い、その後に１５０～２００℃の範囲で２段階目の前処理工程を行ってもよい。
　更に、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
　加熱工程は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す、減圧下で行う等により、低酸素濃度の雰囲気で行うことが特定樹脂の分解を防ぐ点で好ましい。酸素濃度は、５０ｐｐｍ（体積比）以下が好ましく、２０ｐｐｍ（体積比）以下がより好ましい。
　加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。 The heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
＜現像後露光工程＞
　現像工程により得られた（リンス工程を行う場合は、リンス後のパターン）は、上記加熱工程に加えて、現像工程後のパターンを露光する現像後露光工程に供されてもよい。
　すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを露光する現像後露光工程を含んでもよい。本発明の硬化物の製造方法は、加熱工程及び現像後露光工程を含んでもよいし、加熱工程及び現像後露光工程の一方のみを含んでもよい。
　現像後露光工程においては、例えば、光塩基発生剤の感光によってポリイミド前駆体等の環化が進行する反応や、光酸発生剤の感光によって酸分解性基の脱離が進行する反応などを促進することができる。
　現像後露光工程においては、現像工程において得られたパターンの少なくとも一部が露光されればよいが、上記パターンの全部が露光されることが好ましい。
　現像後露光工程における露光量は、感光性化合物が感度を有する波長における露光エネルギー換算で、５０～２０，０００ｍＪ／ｃｍ２であることが好ましく、１００～１５，０００ｍＪ／ｃｍ２であることがより好ましい。
　現像後露光工程は、例えば、上述の露光工程における光源を用いて行うことができ、ブロードバンド光を用いることが好ましい。 <Exposure process after development>
The obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a post-development exposure step for exposing the pattern after the developing step in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like is promoted by exposure to a photobase generator or a reaction in which desorption of acid-degradable groups is promoted by exposure to a photoacid generator is promoted. can do.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
＜金属層形成工程＞
　現像工程により得られたパターン（加熱工程及び露光後現像工程の少なくとも一方に供されたものが好ましい）は、パターン上に金属層を形成する金属層形成工程に供されてもよい。
　すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターン（加熱工程に供されたものが好ましい）上に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
The pattern obtained by the developing step (preferably those subjected to at least one of the heating step and the post-exposure developing step) may be subjected to the metal layer forming step of forming the metal layer on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one subjected to a heating step).
　金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金、タングステン、錫、銀及びこれらの金属を含む合金が例示され、銅及びアルミニウムがより好ましく、銅が更に好ましい。 As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing these metals are exemplified. Copper and aluminum are more preferred, and copper is even more preferred.
　金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開２００７－１５７８７９号公報、特表２００１－５２１２８８号公報、特開２００４－２１４５０１号公報、特開２００４－１０１８５０号公報、米国特許第７８８８１８１Ｂ２、米国特許第９１７７９２６Ｂ２に記載された方法を使用することができる。例えば、フォトリソグラフィ、ＰＶＤ（物理蒸着法）、ＣＶＤ（化学気相成長法）、リフトオフ、電解めっき、無電解めっき、エッチング、印刷、及びこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィ及びエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解めっきを組み合わせたパターニング方法が挙げられる。めっきの好ましい態様としては、硫酸銅やシアン化銅めっき液を用いた電解めっきが挙げられる。 The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.
　金属層の厚さとしては、最も厚肉の部分で、０．０１～５０μｍが好ましく、１～１０μｍがより好ましい。 The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm in the thickest portion.
＜用途＞
　本発明の硬化物の製造方法、又は、本発明の硬化物の適用可能な分野としては、電子デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料（フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜）、又は上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス＆テクノロジー（株）「ポリイミドの高機能化と応用技術」２００８年４月、柿本雅明／監修、ＣＭＣテクニカルライブラリー「ポリイミド材料の基礎と開発」２０１１年１１月発行、日本ポリイミド・芳香族系高分子研究会／編「最新ポリイミド　基礎と応用」エヌ・ティー・エス，２０１０年８月等を参照することができる。 <Use>
Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.
　また、本発明の硬化物の製造方法、又は、本発明の硬化物は、オフセット版面又はスクリーン版面などの版面の製造、成形部品のエッチングへの使用、エレクトロニクス、特に、マイクロエレクトロニクスにおける保護ラッカー及び誘電層の製造などにも用いることもできる。 Further, the method for producing a cured product of the present invention, or the cured product of the present invention, is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
　また、本発明の硬化物の製造方法により得られる硬化物の膜厚は、例えば、硬化物の絶縁性等の観点から、５μｍ以上であることが好ましく、１０μｍ以上がより好ましく、１５μｍ以上がより好ましく、２０μｍ以上が特に好ましい。上記膜厚の上限は特に限定されないが、例えば、５０μｍ以下とすることができる。
　本発明の硬化物の製造方法によれば、このような比較的膜厚が厚い場合であっても解像性に優れた硬化物を製造することができる。 Further, the film thickness of the cured product obtained by the method for producing the cured product of the present invention is preferably 5 μm or more, more preferably 10 μm or more, and more preferably 15 μm or more, for example, from the viewpoint of the insulating property of the cured product. It is preferable, and 20 μm or more is particularly preferable. The upper limit of the film thickness is not particularly limited, but can be, for example, 50 μm or less.
According to the method for producing a cured product of the present invention, it is possible to produce a cured product having excellent resolution even when the film thickness is relatively thick.
（積層体、及び、積層体の製造方法）
　本発明の積層体とは、本発明の硬化物からなる層を複数層有する構造体をいう。
　本発明の積層体は、硬化物からなる層を２層以上含む積層体であり、３層以上積層した積層体としてもよい。
　上記積層体に含まれる２層以上の上記硬化物からなる層のうち、少なくとも１つが本発明の硬化物からなる層であり、硬化物の収縮、又は、上記収縮に伴う硬化物の変形等を抑制する観点からは、上記積層体に含まれる全ての硬化物からなる層が本発明の硬化物からなる層であることも好ましい。 (Laminated body and method for manufacturing the laminated body)
The laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
Of the two or more layers made of the cured product contained in the laminated body, at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
　すなわち、本発明の積層体の製造方法は、本発明の硬化物の製造方法を含むことが好ましく、本発明の硬化物の製造方法を複数回繰り返すことを含むことがより好ましい。 That is, the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.
　本発明の積層体は、硬化物からなる層を２層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む態様が好ましい。上記金属層は、上記金属層形成工程により形成されることが好ましい。
　すなわち、本発明の積層体の製造方法は、複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含むことが好ましい。金属層形成工程の好ましい態様は上述の通りである。
　上記積層体としては、例えば、第一の硬化物からなる層、金属層、第二の硬化物からなる層の３つの層がこの順に積層された層構造を少なくとも含む積層体が好ましいものとして挙げられる。
　上記第一の硬化物からなる層及び上記第二の硬化物からなる層は、いずれも本発明の硬化物からなる層であることが好ましい。上記第一の硬化物からなる層の形成に用いられる本発明の樹脂組成物と、上記第二の硬化物からなる層の形成に用いられる本発明の樹脂組成物とは、組成が同一の組成物であってもよいし、組成が異なる組成物であってもよい。本発明の積層体における金属層は、再配線層などの金属配線として好ましく用いられる。 It is preferable that the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times. The preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
＜積層工程＞
　本発明の積層体の製造方法は、積層工程を含むことが好ましい。
　積層工程とは、パターン（樹脂層）又は金属層の表面に、再度、（ａ）膜形成工程（層形成工程）、（ｂ）露光工程、（ｃ）現像工程、（ｄ）加熱工程を、この順に行うことを含む一連の工程である。ただし、（ａ）の膜形成工程および（ｄ）加熱工程を繰り返す態様であってもよい。また、（ｄ）加熱工程の後には（ｅ）金属層形成工程を含んでもよい。積層工程には、更に、上記乾燥工程等を適宜含んでいてもよいことは言うまでもない。 <Laminating process>
The method for producing a laminated body of the present invention preferably includes a laminating step.
The laminating step is a process of (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step again on the surface of the pattern (resin layer) or metal layer. It is a series of steps including performing in this order. However, it may be an embodiment in which the film forming step (a) and the heating step (d) are repeated. Further, (d) the heating step may be followed by (e) a metal layer forming step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
　積層工程後、更に積層工程を行う場合には、上記露光工程後、上記加熱工程の後、又は、上記金属層形成工程後に、更に、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。表面活性化処理の詳細については後述する。 When the laminating step is further performed, the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
　上記積層工程は、２～２０回行うことが好ましく、２～９回行うことがより好ましい。
　例えば、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層のように、樹脂層を２層以上２０層以下とする構成が好ましく、２層以上９層以下とする構成が更に好ましい。
　上記各層はそれぞれ、組成、形状、膜厚等が同一であってもよいし、異なっていてもよい。 The laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a structure having two or more and 20 or less resin layers, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
The composition, shape, film thickness, etc. of each of the above layers may be the same or different.
　本発明では特に、金属層を設けた後、更に、上記金属層を覆うように、上記本発明の樹脂組成物の硬化物（樹脂層）を形成する態様が好ましい。具体的には、（ａ）膜形成工程、（ｂ）露光工程、（ｃ）現像工程、（ｄ）加熱工程（ｅ）金属層形成工程、の順序で繰り返す態様、又は、（ａ）膜形成工程、（ｄ）加熱工程、（ｅ）金属層形成工程の順序で繰り返す態様が挙げられる。本発明の樹脂組成物層（樹脂層）を積層する積層工程と、金属層形成工程を交互に行うことにより、本発明の樹脂組成物層（樹脂層）と金属層を交互に積層することができる。 In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (d) a heating step (e) a metal layer forming step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which the step, (d) heating step, and (e) metal layer forming step are repeated in this order. By alternately performing the laminating step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated. can.
（表面活性化処理工程）
　本発明の積層体の製造方法は、上記金属層および樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含むことが好ましい。
　表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記加熱工程の後、樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。  
　表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、加熱後の樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および加熱後の樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂組成物層（膜）との密着性を向上させることができる。
　また、表面活性化処理は、露光後の樹脂組成物層（樹脂層）の一部または全部についても行うことが好ましい。このように、樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。特にネガ型現像を行う場合など、樹脂組成物層が硬化されている場合には、表面処理によるダメージを受けにくく、密着性が向上しやすい。
　表面活性化処理としては、具体的には、各種原料ガス（酸素、水素、アルゴン、窒素、窒素／水素混合ガス、アルゴン／酸素混合ガスなど）のプラズマ処理、コロナ放電処理、ＣＦ４／Ｏ２、ＮＦ３／Ｏ２、ＳＦ６、ＮＦ３、ＮＦ３／Ｏ２によるエッチング処理、紫外線（ＵＶ）オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、５００～２００，０００Ｊ／ｍ２が好ましく、１０００～１００，０００Ｊ／ｍ２がより好ましく、１０，０００～５０，０００Ｊ／ｍ２が最も好ましい。 (Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the heating step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the heated resin composition layer, or on the metal layer and the heated resin composition layer. For both, you may go to at least part of each. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment. In particular, when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 . , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. In the case of the corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
（電子デバイスの製造方法）
　本発明は、本発明の硬化物の製造方法、又は、本発明の積層体の製造方法を含む半導体デバイスの製造方法も開示する。本発明の樹脂組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開２０１６－０２７３５７号公報の段落０２１３～０２１８の記載及び図１の記載を参酌でき、これらの内容は本明細書に組み込まれる。 (Manufacturing method of electronic device)
The present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention. As specific examples of the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
（樹脂組成物）
　本発明の樹脂組成物は、本発明の硬化物の製造方法において用いられる樹脂組成物である。
　本発明の樹脂組成物は、樹脂、活性光線又は放射線の照射により酸を発生する化合物、及び、溶剤、を含み、上記樹脂はポリイミド前駆体であり、上記樹脂は酸の作用により極性が増大する反応を生じる基を有する。
　以下、本発明の樹脂組成物に含まれる、各成分の詳細について説明する。 (Resin composition)
The resin composition of the present invention is a resin composition used in the method for producing a cured product of the present invention.
The resin composition of the present invention contains a resin, a compound that generates an acid by irradiation with active light or radiation, and a solvent. The resin is a polyimide precursor, and the polarity of the resin is increased by the action of the acid. It has a group that causes a reaction.
Hereinafter, details of each component contained in the resin composition of the present invention will be described.
＜樹脂＞
　樹脂組成物は、ポリイミド前駆体であり、酸の作用により極性が増大する反応を生じる基（極性変換基）を有する樹脂を含む。
　極性変換基としては、酸分解性基が挙げられ、酸の作用により分解しアルカリ可溶性基を生じる基が好ましい。
　酸分解性基としては、アセタール基、シリル基、シリルエーテル基、第三級アルキルエステル基等が挙げられ、アセタール基、又は、第三級アルキルエステル基が好ましく、露光感度の観点からは、アセタール基がより好ましい。 <Resin>
The resin composition is a polyimide precursor and contains a resin having a group (polarity converting group) that causes a reaction in which the polarity is increased by the action of an acid.
Examples of the polar conversion group include an acid-degradable group, and a group that decomposes by the action of an acid to form an alkali-soluble group is preferable.
Examples of the acid-decomposable group include an acetal group, a silyl group, a silyl ether group, a tertiary alkyl ester group and the like, and an acetal group or a tertiary alkyl ester group is preferable, and an acetal group is preferable from the viewpoint of exposure sensitivity. Groups are more preferred.
　これらの中でも、極性変換基は、下記式（Ａ－１）又は下記式（Ａ－２）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000005
 　式（Ａ－１）中、ＲＡ１～ＲＡ５はそれぞれ独立に、水素原子又は１価の有機基を表し、ＲＡ１～ＲＡ５のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す；
　式（Ａ－２）中、ＲＡ６～ＲＡ８はそれぞれ独立に、１価の有機基を表し、ＲＡ６～ＲＡ８のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す。 Among these, the polarity converting group is preferably a group represented by the following formula (A-1) or the following formula (A-2).
Figure JPOXMLDOC01-appb-C000005
 In the formula (A-1), RA1 to RA5 each independently represent a hydrogen atom or a monovalent organic group, and even if at least two of RA1 to RA5 are bonded to form a ring structure. Often, * represents the binding site with other structures;
In the formula (A-2), RA6 to RA8 each independently represent a monovalent organic group, and at least two of RA6 to RA8 may be bonded to form a ring structure *. Represents a binding site with another structure.
　式（Ａ－１）中、ＲＡ１及びＲＡ２はそれぞれ独立に、水素原子又は１価の有機基を表し、水素原子又は１価の炭化水素基が好ましい。１価の炭化水素基としては、脂肪族炭化水素基、芳香族多価水素基、又はこれらの結合により表される基のいずれであってもよいが、脂肪族炭化水素基、又は、脂肪族炭化水素基及び芳香族炭化水素基の結合により表される基であることが好ましく、飽和脂肪族炭化水素基、又は、飽和脂肪族炭化水素基及び芳香族炭化水素基の結合により表される基であることが好ましい。
　式（Ａ－１）中、ＲＡ３～ＲＡ５はそれぞれ独立に、水素原子又は１価の有機基を表し、水素原子又は１価の炭化水素基が好ましく、水素原子がより好ましい。
　また、式（Ａ－１）中、ＲＡ１～ＲＡ５のうち少なくとも２つが結合して環構造を形成する場合、ＲＡ１及びＲＡ２の少なくとも一方と、ＲＡ３～ＲＡ５の少なくとも１つとが結合して環構造を形成することが好ましい。形成される環構造としては、テトラヒドロフラン環等が挙げられる。
　式（Ａ－２）中、ＲＡ６～ＲＡ８はそれぞれ独立に、１価の有機基を表し、１価の炭化水素基を表すことが好ましく、炭素数１～１０の１価の炭化水素基を表すことがより好ましく、炭素数１～４の１価の炭化水素基を表すことが更に好ましく、炭素数１～４のアルキル基を表すことが特に好ましい。
　ＲＡ６～ＲＡ８のうち少なくとも２つが結合して環構造を形成する場合、環構造としては特に限定されないが、脂肪族炭化水素環構造であることが好ましく、飽和脂肪族炭化水素環構造であることがより好ましい。 In the formula ( A -1), RA1 and RA2 independently represent a hydrogen atom or a monovalent organic group, and a hydrogen atom or a monovalent hydrocarbon group is preferable. The monovalent hydrocarbon group may be any of an aliphatic hydrocarbon group, an aromatic polyhydric group, or a group represented by a bond thereof, but is an aliphatic hydrocarbon group or an aliphatic group. It is preferably a group represented by a bond of a hydrocarbon group and an aromatic hydrocarbon group, and is a saturated aliphatic hydrocarbon group or a group represented by a bond of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group. Is preferable.
In the formula (A-1), RA3 to RA5 independently represent a hydrogen atom or a monovalent organic group, a hydrogen atom or a monovalent hydrocarbon group is preferable, and a hydrogen atom is more preferable.
Further, in the formula (A-1), when at least two of RA1 to RA5 are combined to form a ring structure, at least one of RA1 and RA2 and at least one of RA3 to RA5 are present. It is preferable to combine them to form a ring structure. Examples of the ring structure formed include a tetrahydrofuran ring and the like.
In the formula (A-2), RA6 to RA8 independently represent a monovalent organic group, preferably a monovalent hydrocarbon group, and a monovalent hydrocarbon group having 1 to 10 carbon atoms. It is more preferable to represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, and it is particularly preferable to represent an alkyl group having 1 to 4 carbon atoms.
When at least two of RA6 to RA8 are bonded to form a ring structure, the ring structure is not particularly limited, but an aliphatic hydrocarbon ring structure is preferable, and a saturated aliphatic hydrocarbon ring structure is used. Is more preferable.
〔ポリイミド前駆体〕
　本発明で用いるポリイミド前駆体は、下記式（１）で表される繰返し単位を含むことが好ましい。 [Polyimide precursor]
The polyimide precursor used in the present invention preferably contains a repeating unit represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（１）中、
　Ｒ１は、４価の有機基を表す。複数のＲ１は互いに同一であっても異なっていてもよい。
　Ｒ２は、２価の有機基を表す。複数のＲ２は互いに同一であっても異なっていてもよい。
　Ｒ３は、各々独立に、水素原子又は有機基を表す。
　式（１）で表される繰返し単位は、極性変換基を含むことが好ましく、式（１）における複数の－ＣＯ２Ｒ３のうち少なくとも１つは、極性変換基を含む基であることがより好ましく、式（１）における複数の－ＣＯ２Ｒ３のうち少なくとも１つは、酸の作用により分解しアルカリ可溶性基を生じる基であることが更に好ましい。 In the above formula (1),
R 1 represents a tetravalent organic group. The plurality of R 1s may be the same as or different from each other.
R 2 represents a divalent organic group. The plurality of R 2s may be the same as or different from each other.
R 3 independently represents a hydrogen atom or an organic group.
The repeating unit represented by the formula (1) preferably contains a polarity converting group, and at least one of the plurality of —CO 2 R 3 in the formula (1) is a group containing a polarity converting group. More preferably, at least one of the plurality of -CO 2 R 3 in the formula (1) is a group which is decomposed by the action of an acid to produce an alkali-soluble group.
　また、上記式（１）で表される繰り返し単位が、上述の式（Ａ－１）又は式（Ａ－２）で表される基を含むことが好ましい。
　式（１）で表される繰り返し単位が、上述の式（Ａ－１）で表される基を含む場合、式（１）中のＲ３が下記式（Ａ’－１）で表される基であることにより、式（１）で表される繰り返し単位が、上述の式（Ａ－１）で表される基を含むことが好ましい。
　また、式（１）で表される繰り返し単位が、上述の式（Ａ－２）で表される基を含む場合、式（１）中Ｒ３が下記式（Ａ’－２）であることにより、式（１）で表される繰り返し単位が、上述の式（Ａ－２）で表される基を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000007
 　式（Ａ’－１）中、ＲＡ１～ＲＡ５はそれぞれ、式（Ａ－１）中のＲＡ１～ＲＡ５と同義であり、好ましい態様も同様である。また、＊は式（１）中のＲ３が結合する酸素原子との結合部位を表す。
　式（Ａ’－２）中、ＲＡ６～ＲＡ８はそれぞれ、式（Ａ－２）中のＲＡ６～ＲＡ８と同義であり、好ましい態様も同様である。また、＊は式（１）中のＲ３が結合する酸素原子との結合部位を表す。 Further, it is preferable that the repeating unit represented by the above formula (1) contains a group represented by the above formula (A-1) or the above formula (A-2).
When the repeating unit represented by the formula (1) includes the group represented by the above formula (A-1), R 3 in the formula (1) is represented by the following formula (A'-1). By being a group, it is preferable that the repeating unit represented by the formula (1) includes the group represented by the above formula (A-1).
Further, when the repeating unit represented by the formula (1) includes the group represented by the above formula (A- 2 ), R3 in the formula (1) is the following formula (A'-2). Therefore, it is preferable that the repeating unit represented by the formula (1) contains the group represented by the above formula (A-2).
Figure JPOXMLDOC01-appb-C000007
 In the formula (A'-1), RA1 to RA5 are synonymous with RA1 to RA5 in the formula (A-1), respectively, and the preferred embodiments are also the same. Further, * represents a binding site with an oxygen atom to which R 3 in the formula (1) is bonded.
In the formula (A'-2), RA6 to RA8 are synonymous with RA6 to RA8 in the formula (A-2), respectively, and the preferred embodiments are also the same. Further, * represents a binding site with an oxygen atom to which R 3 in the formula (1) is bonded.
　式（１）で表される繰返し単位を有する樹脂は、酸の作用によりアルカリ現像液に対する溶解度が増大する樹脂である。式（１）の繰返し単位を有する樹脂は、好ましくはアルカリ現像液に不溶又は難溶性である。 The resin having the repeating unit represented by the formula (1) is a resin whose solubility in an alkaline developer is increased by the action of an acid. The resin having the repeating unit of the formula (1) is preferably insoluble or sparingly soluble in an alkaline developer.
　式（１）で表される繰返し単位は、Ｒ１を核として４個のカルボキシ基を有する化合物、そのカルボン酸無水物、又は上記４個のカルボキシ基のうちの少なくとも１つにおける水素原子が酸の作用により脱離する基で置換されてなる化合物に由来する酸成分と、Ｒ２を核として２個のアミノ基を有する化合物に由来するジアミン成分とから構成される。換言すると、式（１）中の２つのカルボニル基で挟まれた上記２つのカルボニル基を含む部分構造である酸成分と、式（１）中の－ＮＨ－Ｒ２－ＮＨ－で表される部分構造であるジアミン成分とから構成される。
　４価の有機基Ｒ１としては、炭素数４～３０であることが好ましく、単環式又は縮合多環式の脂肪族基又は芳香族基を有する４価の連結基であることがより好ましい。複数のＲ１は互いに同一であっても異なっていてもよい。
　４価の有機基Ｒ１における単環式の芳香族基としては、ベンゼン環基、ピリジン環基等が挙げられる。
　４価の有機基Ｒ１における縮合多環式の芳香族基としては、ナフタレン環基、ペリレン環基などが挙げられる。
　４価の有機基Ｒ１における単環式の脂肪族基としては、シクロブタン環基、シクロペンタン環基、シクロへキサン環基などが挙げられる。
　４価の有機基Ｒ１における縮合多環式の脂肪族基としては、ビシクロ［２．２．１］へプタン環基、ビシクロ［２．２．２］オクタン環基、ビシクロ［２．２．２］オクト－７－エン環基などが挙げられる。
　４価の有機基Ｒ１についての単環式又は縮合多環式の脂肪族基又は芳香族基を有する４価の連結基としては、上述の単環式又は縮合多環式の脂肪族基又は芳香族基そのものであってもよいが、複数の単環式又は縮合多環式の脂肪族基又は芳香族基が単結合ないしは２価の連結基を介して連結して、Ｒ１としての４価の連結基を形成していてもよい。
　上記２価の連結基としては、アルキレン基（炭素数１～６のアルキレン基が好ましく、例えば、メチレン基、エチレン基、プロピレン基など）、酸素原子、イオウ原子、２価のスルホン基、エステル結合、ケトン基、アミド基などが挙げられる。 In the repeating unit represented by the formula (1), a compound having four carboxy groups with R 1 as a nucleus, an carboxylic acid anhydride thereof, or a hydrogen atom in at least one of the above four carboxy groups is an acid. It is composed of an acid component derived from a compound substituted with a group desorbed by the action of the above, and a diamine component derived from a compound having two amino groups with R2 as a nucleus. In other words, it is represented by an acid component which is a partial structure containing the above two carbonyl groups sandwiched between the two carbonyl groups in the formula (1) and -NH-R 2 -NH- in the formula (1). It is composed of a diamine component, which is a partial structure.
The tetravalent organic group R1 preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. .. The plurality of R 1s may be the same as or different from each other.
Examples of the monocyclic aromatic group in the tetravalent organic group R 1 include a benzene ring group and a pyridine ring group.
Examples of the fused polycyclic aromatic group in the tetravalent organic group R 1 include a naphthalene ring group and a perylene ring group.
Examples of the monocyclic aliphatic group in the tetravalent organic group R 1 include a cyclobutane ring group, a cyclopentane ring group, a cyclohexane ring group and the like.
Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R 1 include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] Oct-7-ene ring group and the like can be mentioned.
As the tetravalent linking group having a monocyclic or fused polycyclic aliphatic group or aromatic group for the tetravalent organic group R 1 , the above-mentioned monocyclic or condensed polycyclic aliphatic group or the above-mentioned monocyclic or condensed polycyclic aliphatic group or The aromatic group itself may be used, but a plurality of monocyclic or fused polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group to form 4 as R1 . It may form a linking group of valences.
The divalent linking group is preferably an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, etc.), an oxygen atom, a sulfur atom, a divalent sulfone group, and an ester bond. , Ketone group, amide group and the like.
　Ｒ１を核として少なくとも４個のカルボキシ基に由来する基を有する酸成分の具体例としては、ピロメリット酸無水物、３，３’，４，４’－ビフェニルテトラカルボン酸無水物、２，３，３’，４’－ビフェニルテトラカルボン酸無水物、２，２’，３，３’－ビフェニルテトラカルボン酸無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸無水物、２，２’，３，３’－ベンゾフェノンテトラカルボン酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）二フタル酸無水物、１，２，５，６－ナフタレンテトラカルボン酸無水物、２，３，６，７－ナフタレンテトラカルボン酸無水物、２，３，５，６－ピリジンテトラカルボン酸無水物、３，４，９，１０－ペリレンテトラカルボン酸無水物、（トリフルオロメチル）ピロメリット酸無水物、ジ（トリフルオロメチル）ピロメリット酸無水物、ジ（ヘプタフルオロプロピル）ピロメリット酸無水物、ペンタフルオロエチルピロメリット酸無水物、ビス〔３、５－ジ（トリフルオロメチル）フェノキシ〕ピロメリット酸無水物、３，３’，４，４’－テトラカルボキシジフェニルエーテル二無水物、２，３’，３，４’－テトラカルボキシジフェニルエーテル二無水物、３，３’，４，４’－テトラカルボキシジフェニルメタン二無水物、３，３’，４，４’－テトラカルボキシジフェニルスルホン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、５，５’－ビス（トリフルオロメチル）－３，３’，４，４’－テトラカルボキシビフェニル二無水物、２，２’，５，５’－テトラキス（トリフルオロメチル）－３，３’，４，４’－テトラカルボキシビフェニル二無水物、５，５’－ビス（トリフルオロメチル）－３，３’，４，４’－テトラカルボキシジフェニルエーテル二無水物、５，５’－ビス（トリフルオロメチル）－３，３’，４，４’－テトラカルボキシベンゾフェノン二無水物、ビス〔（トリフルオロメチル）ジカルボキシフェノキシ〕ベンゼン二無水物、ビス（ジカルボキシフェノキシ）ビス（トリフルオロメチル）ベンゼン二無水物、ビス（ジカルボキシフェノキシ）テトラキス（トリフルオロメチル）ベンゼン二無水物、２，２－ビス〔４－（３，４－ジカルボキシフェノキシ）フェニル〕プロパン二無水物、２，２－ビス（４－（３，４－ジカルボキシフェノキシ）フェニル）ヘキサフルオロプロパン二無水物、５，５’－［ｐ－フェニレンビス（オキシカルボニル）］ジ無水フタル酸などの芳香族テトラカルボン酸無水物に由来する成分や、シクロブタンテトラカルボン酸無水物、シクロペンタンテトラカルボン酸無水物、シクロヘキサンテトラカルボン酸無水物、１，２，４，５－シクロヘキサンテトラカルボン酸、ビシクロ［２．２．１］へプタン－２，３，５，６－テトラカルボン酸、ビシクロ［２．２．２］オクタン－２，３，５，６－テトラカルボン酸、又はビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸、ビシクロ［２．２．２］オクタン－２，３，５，６－テトラカルボン酸二無水物、（１Ｓ，２Ｓ，４Ｒ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物、（１Ｒ，２Ｓ，４Ｓ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物などの脂肪族テトラカルボン酸無水物に由来する成分などが挙げられる。 Specific examples of the acid component having a group derived from at least four carboxy groups with R1 as a nucleus include pyromellitic acid anhydride, 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 2, 3,3', 4'-biphenyltetracarboxylic acid anhydride, 2,2', 3,3'-biphenyltetracarboxylic acid anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid anhydride, 2 , 2', 3,3'-benzophenone tetracarboxylic acid anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride, 1,2,5,6-naphthalenetetracarboxylic acid anhydride, 2, 3,6,7-naphthalenetetracarboxylic acid anhydride, 2,3,5,6-pyridinetetracarboxylic acid anhydride, 3,4,9,10-perylenetetracarboxylic acid anhydride, (trifluoromethyl) pyromerit Acid anhydride, di (trifluoromethyl) pyromellitic anhydride, di (heptafluoropropyl) pyromellitic anhydride, pentafluoroethyl pyromellitic anhydride, bis [3,5-di (trifluoromethyl) phenoxy ] Pyromellitic anhydride, 3,3', 4,4'-tetracarboxydiphenyl ether dianhydride, 2,3', 3,4'-tetracarboxydiphenyl ether dianhydride, 3,3', 4,4' -Tetracarboxydiphenylmethane dianhydride, 3,3', 4,4'-tetracarboxydiphenylsulfonate dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-Dicarboxyphenyl) Hexafluoropropane dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 2,2', 5,5'-Tetrakiss (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl anhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4' -Tetracarboxydiphenylether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis [(trifluoromethyl) dicarboxyphenoxy] benzenedi Anhydrous, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2,2-bis [4- (3,4-) Dicarboxyphenoxy) phenyl] propane dianhydride , 2,2-Bis (4- (3,4-dicarboxyphenoxy) phenyl) Hexafluoropropane dianhydride, 5,5'-[p-phenylenebis (oxycarbonyl)] Dianophilic phthalic acid and other aromatics Ingredients derived from tetracarboxylic acid anhydride, cyclobutanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2. 2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, or bicyclo [2.2.2] Oct-7-en-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, (1S, 2S, 4R, Examples thereof include components derived from aliphatic tetracarboxylic acid anhydrides such as 5R) -cyclohexanetetracarboxylic acid dianhydride and (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride.
　好ましくは、ピロメリット酸無水物に由来する成分、３，３’，４，４’－ビフェニルテトラカルボン酸無水物に由来する成分、２，３，３’，４’－ビフェニルテトラカルボン酸無水物に由来する成分、２，２’，３，３’－ビフェニルテトラカルボン酸無水物に由来する成分、３，３’，４，４’－ベンゾフェノンテトラカルボン酸無水物に由来する成分、４，４’－（ヘキサフルオロイソプロピリデン）二フタル酸無水物に由来する成分、３，３’，４，４’－テトラカルボキシジフェニルエーテル二無水物に由来する成分、１，２，５，６－ナフタレンテトラカルボン酸無水物に由来する成分、５，５’－［ｐ－フェニレンビス（オキシカルボニル）］ジ無水フタル酸に由来する成分、シクロブタンテトラカルボン酸無水物に由来する成分、シクロペンタンテトラカルボン酸無水物に由来する成分、ビシクロ［２．２．２］オクタン－２，３，５，６－テトラカルボン酸二無水物に由来する成分、（１Ｓ，２Ｓ，４Ｒ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物に由来する成分、（１Ｒ，２Ｓ，４Ｓ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物に由来する成分であり、より好ましくはピロメリット酸無水物に由来する成分、３，３’，４，４’－ビフェニルテトラカルボン酸無水物に由来する成分、４，４’－（ヘキサフルオロイソプロピリデン）二フタル酸無水物に由来する成分、シクロブタンテトラカルボン酸無水物に由来する成分、３，３’，４，４’－テトラカルボキシジフェニルエーテル二無水物に由来する成分、シクロペンタンテトラカルボン酸無水物に由来する成分、５，５’－［ｐ－フェニレンビス（オキシカルボニル）］ジ無水フタル酸に由来する成分、（１Ｓ，２Ｓ，４Ｒ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物に由来する成分、（１Ｒ，２Ｓ，４Ｓ，５Ｒ）－シクロヘキサンテトラカルボン酸二無水物に由来する成分である。これらを使用することによって良好な溶剤溶解性、アルカリ溶解速度、透明性、応力特性が実現できる。
　Ｒ１を核として４個のカルボキシ基を有する化合物などに由来する酸成分の樹脂における含有量としては、樹脂を構成する全繰返し単位に対して２０～７０モル％であることが好ましく、３０～６０モル％であることがより好ましい。 Preferably, a component derived from pyromellitic anhydride, a component derived from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 2,3,3', 4'-biphenyltetracarboxylic acid anhydride. , 2', 3,3'-components derived from biphenyltetracarboxylic acid anhydride, 3,3', 4,4'-components derived from benzophenone tetracarboxylic acid anhydride, 4,4 '-(Hexafluoroisopropylidene) component derived from diphthalic anhydride, 3,3', 4,4'-tetracarboxydiphenyl ether component derived from dianhydride, 1,2,5,6-naphthalenetetracarboxylic Component derived from acid anhydride, component derived from 5,5'-[p-phenylenebis (oxycarbonyl)] dianhydride phthalic acid, component derived from cyclobutanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride Ingredients derived from, Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid dianhydride A component derived from a substance, a component derived from (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride, more preferably a component derived from pyromellitic acid anhydride, 3, 3', 4, 4'-Component derived from biphenyltetracarboxylic acid anhydride, 4,4'-(hexafluoroisopropylidene) component derived from diphthalic acid anhydride, component derived from cyclobutanetetracarboxylic acid anhydride, 3,3' , 4,4'-Component derived from tetracarboxydiphenyl ether dianhydride, component derived from cyclopentanetetracarboxylic acid anhydride, 5,5'-[p-phenylenebis (oxycarbonyl)] derived from phthalic anhydride A component derived from (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid dianhydride, and a component derived from (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride. By using these, good solvent solubility, alkali dissolution rate, transparency, and stress characteristics can be realized.
The content of the acid component derived from a compound having four carboxy groups with R1 as a core in the resin is preferably 20 to 70 mol%, preferably 30 to 70 mol% with respect to all the repeating units constituting the resin. More preferably, it is 60 mol%.
　式（１）におけるＲ２は、２価の有機基を表す。２価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数２～２０の直鎖又は分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数３～２０の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、－Ａｒ－および－Ａｒ－Ｌ－Ａｒ－で表される基であることが例示され、特に好ましくは－Ａｒ－Ｌ－Ａｒ－で表される基である。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、単結合、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－又は－ＮＨＣＯ－、あるいは、上記の２つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 R 2 in the formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group. Preferred embodiments of the present invention exemplify the groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably the groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-,. -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.
　Ｒ２は、ジアミンから誘導されることが好ましい。上記樹脂の製造に用いられるジアミンとしては、直鎖又は分岐の脂肪族、環状の脂肪族又は芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。
具体的には、炭素数２～２０の直鎖又は分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数３～２０の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数６～２０の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。 R 2 is preferably derived from diamine. Examples of the diamine used for producing the resin include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group. Examples of groups containing aromatic groups include:
Figure JPOXMLDOC01-appb-C000008
 　式中、Ａは単結合又は２価の連結基を表し、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ２－、ＮＨＣＯ－、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、又は、－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、又は、－Ｃ（ＣＨ３）２－であることが更に好ましい。
　式中、＊は他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000008
 In the formula, A represents a single bond or a divalent linking group, which is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (=). O)-, -S-, -SO 2- , NHCO-, or a group selected from a combination thereof is preferable, and it is a single bond or a group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. More preferably, it is a group selected from an alkylene group, -O-, -C (= O)-, -S-, or -SO 2- , and -CH 2- , -O-, -S-, It is more preferably -SO 2- , -C (CF 3 ) 2- , or -C (CH 3 ) 2- .
In the formula, * represents a binding site with another structure.
　ジアミンとしては、具体的には、１，２－ジアミノエタン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタン及び１，６－ジアミノヘキサン；１，２－又は１，３－ジアミノシクロペンタン、１，２－、１，３－又は１，４－ジアミノシクロヘキサン、１，２－、１，３－又は１，４－ビス（アミノメチル）シクロヘキサン、ビス－（４－アミノシクロヘキシル）メタン、ビス－（３－アミノシクロヘキシル）メタン、４，４’－ジアミノ－３，３’－ジメチルシクロヘキシルメタン及びイソホロンジアミン；ｍ－又はｐ－フェニレンジアミン、ジアミノトルエン、４，４’－又は３，３’－ジアミノビフェニル、４，４’－ジアミノジフェニルエーテル、３，３－ジアミノジフェニルエーテル、４，４’－及び３，３’－ジアミノジフェニルメタン、４，４’－及び３，３’－ジアミノジフェニルスルホン、４，４’－及び３，３’－ジアミノジフェニルスルフィド、４，４’－又は３，３’－ジアミノベンゾフェノン、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、４，４’－ジアミノパラテルフェニル、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（２－アミノフェノキシ）フェニル］スルホン、１，４－ビス（４－アミノフェノキシ）ベンゼン、９，１０－ビス（４－アミノフェニル）アントラセン、３，３’－ジメチル－４，４’－ジアミノジフェニルスルホン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェニル）ベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、４，４’－ジアミノオクタフルオロビフェニル、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）－１０－ヒドロアントラセン、３，３’，４，４’－テトラアミノビフェニル、３，３’，４，４’－テトラアミノジフェニルエーテル、１，４－ジアミノアントラキノン、１，５－ジアミノアントラキノン、３，３－ジヒドロキシ－４，４’－ジアミノビフェニル、９，９’－ビス（４－アミノフェニル）フルオレン、４，４’－ジメチル－３，３’－ジアミノジフェニルスルホン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、２，４－及び２，５－ジアミノクメン、２，５－ジメチル－ｐ－フェニレンジアミン、アセトグアナミン、２，３，５，６－テトラメチル－ｐ－フェニレンジアミン、２，４，６－トリメチル－ｍ－フェニレンジアミン、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（ｐ－アミノフェニル）オクタメチルペンタシロキサン、２，７－ジアミノフルオレン、２，５－ジアミノピリジン、１，２－ビス（４－アミノフェニル）エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、１，５－ジアミノナフタレン、ジアミノベンゾトリフルオライド、１，３－ビス（４－アミノフェニル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェニル）オクタフルオロブタン、１，５－ビス（４－アミノフェニル）デカフルオロペンタン、１，７－ビス（４－アミノフェニル）テトラデカフルオロヘプタン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ジメチルフェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ビス（トリフルオロメチル）フェニル］ヘキサフルオロプロパン、ｐ－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ベンゼン、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４’－ビス（３－アミノ－５－トリフルオロメチルフェノキシ）ジフェニルスルホン、２，２－ビス［４－（４－アミノ－３－トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、３，３’，５，５’－テトラメチル－４，４’－ジアミノビフェニル、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、２，２’，５，５’，６，６’－ヘキサフルオロトリジン及び４，４’－ジアミノクアテルフェニルから選ばれる少なくとも１種のジアミンが挙げられる。 Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-Bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2- Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino) -2-Trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) ) Biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-Amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5' -Tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin And at least one diamine selected from 4,4'-diaminoquaterphenyl.
　また、国際公開第２０１７／０３８５９８号の段落００３０～００３１に記載のジアミン（ＤＡ－１）～（ＤＡ－１８）も好ましい。 Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
　また、国際公開第２０１７／０３８５９８号の段落００３２～００３４に記載の２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましく用いられる。 Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
　Ｒ２は、得られる有機膜の柔軟性の観点から、－Ａｒ－Ｌ－Ａｒ－で表されることが好ましい。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－又はＮＨＣＯ－、あるいは、上記の２つ以上の組み合わせからなる基である。Ａｒは、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１又は２の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－又はＳＯ２－が好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R2 is preferably represented by −Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.
　また、Ｒ２は、ｉ線透過率の観点から、下記式（５１）又は式（６１）で表される２価の有機基であることが好ましい。特に、ｉ線透過率、入手のし易さの観点から、式（６１）で表される２価の有機基であることがより好ましい。
　式（５１）
Figure JPOXMLDOC01-appb-C000009
 　式（５１）中、Ｒ５０～Ｒ５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ５０～Ｒ５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基である。＊は他の構造との結合部位を表す。
　Ｒ５０～Ｒ５７の１価の有機基としては、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
Figure JPOXMLDOC01-appb-C000010
 　式（６１）中、Ｒ５８及びＲ５９は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基である。＊は他の構造との結合部位を表す。
　式（５１）又は（６１）の構造を与えるジアミン化合物としては、２，２’－ジメチルベンジジン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種で又は２種以上を組み合わせて用いてもよい。 Further, R 2 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
Figure JPOXMLDOC01-appb-C000009
 In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group. * Represents a binding site with another structure.
The monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
Figure JPOXMLDOC01-appb-C000010
 In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group. * Represents a binding site with another structure.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
　また、基板との接着性を高めるためにＲ２を核とするジアミン成分としてシリコンジアミン成分とすることができる。この例としては、ビス（４－アミノフェニル）ジメチルシラン成分、ビス（４－アミノフェニル）テトラメチルシロキサン成分、ビス（４－アミノフェニル）テトラメチルジシロキサン成分、ビス（γ―アミノプロピル）テトラメチルジシロキサン成分、１，４－ビス（γ―アミノプロピルジメチルシリル）ベンゼン成分、ビス（４－アミノブチル）テトラメチルジシロキサン成分、ビス（γ―アミノプロピル）テトラフェニルジシロキサン成分等が挙げられる。
　シリコンジアミン成分として、下記構造も挙げることができる。 Further, in order to enhance the adhesiveness with the substrate, a silicon diamine component can be used as the diamine component having R 2 as a core. Examples of this are bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, and bis (γ-aminopropyl) tetramethyl. Examples thereof include a disiloxane component, a 1,4-bis (γ-aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis (γ-aminopropyl) tetraphenyldisiloxane component.
The following structure can also be mentioned as a silicon diamine component.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式において、Ｒ５及びＲ６は２価の有機基を表し、Ｒ７及びＲ８はそれぞれ独立に、１価の有機基を表す。すなわち、複数のＲ７は互いに同一であっても異なっていてもよい。複数のＲ８は互いに同一であっても異なっていてもよい。
　Ｒ５及びＲ６で表される２価の有機基としては、置換基を有していてもよい炭素数１～２０の直鎖もしくは分岐のアルキレン基、炭素数６～２０のフェニレン基、炭素数３～２０の２価の脂環基、又はこれらを組み合わせて構成される基を表す。
　Ｒ７及びＲ８で表される１価の有機基としては、置換基を有していてもよい炭素数１～２０の直鎖もしくは分岐のアルキル基もしくは炭素数６～２０のアリール基を表す。
　より具体的には、下記を挙げることができる。 In the above formula, R 5 and R 6 represent a divalent organic group, and R 7 and R 8 each independently represent a monovalent organic group. That is, the plurality of R 7s may be the same or different from each other. The plurality of R8s may be the same as or different from each other.
Examples of the divalent organic group represented by R5 and R6 include a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, a phenylene group having 6 to 20 carbon atoms, and carbon. It represents a divalent alicyclic group of the number 3 to 20, or a group composed of a combination thereof.
The monovalent organic group represented by R 7 and R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. ..
More specifically, the following can be mentioned.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　特定樹脂において、樹脂中に存在する複数の－ＣＯ２Ｒ３のうち少なくとも１つは、酸の作用により分解しアルカリ可溶性基を生じる基であることが好ましい。
　酸の作用により分解しアルカリ可溶性基を生じる基とは、酸の作用により分解し、樹脂側にヒドロキシ基（例えば、フェノール性ヒドロキシ基）、カルボキシ基のようなアルカリ可溶性基を生じる基（以下、酸分解性基ともいう。）をいう。本発明において、酸分解性基は、酸の作用により分解し、樹脂側にアルカリ可溶性基としてカルボキシ基を生じる基であることが好ましい。
　酸分解性基として好ましい基は、これらのアルカリ可溶性基の水素原子を酸で脱離する基で置換した基である。
　酸で脱離する基としては、例えば、－Ｃ（Ｒ３６）（Ｒ３７）（Ｒ３８）、－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３９）、－Ｃ（Ｒ０１）（Ｒ０２）（ＯＲ３９）等を挙げることができる。　式中、Ｒ３６～Ｒ３９は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。Ｒ３６とＲ３７とは、互いに結合して環を形成してもよい。
　上記アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～５のアルキル基がより好ましい。
　上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
　上記シクロアルキル基としては、炭素数３～１２のシクロアルキル基が好ましく、炭素数３～８のシクロアルキル基がより好ましい。
　上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
　上記アリール基は炭素数６～３０の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
　上記アラルキル基としては、炭素数７～２０のアラルキル基が好ましく、炭素数７～１６のアラルキル基がより好ましい。
　上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
　上記アルケニル基は炭素数３～２０のアルケニル基が好ましく、炭素数３～１６のアルケニル基がより好ましい。
　また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。 In the specific resin, it is preferable that at least one of the plurality of -CO 2 R 3 present in the resin is a group that is decomposed by the action of an acid to produce an alkali-soluble group.
A group that decomposes by the action of an acid to produce an alkali-soluble group is a group that decomposes by the action of an acid and produces an alkali-soluble group such as a hydroxy group (for example, a phenolic hydroxy group) or a carboxy group on the resin side (hereinafter referred to as a group). It is also called an acid-degradable group.) In the present invention, the acid-degradable group is preferably a group that is decomposed by the action of an acid to generate a carboxy group as an alkali-soluble group on the resin side.
A preferred group as an acid-degradable group is a group in which the hydrogen atom of these alkali-soluble groups is replaced with a group that desorbs an acid.
Examples of the group desorbed by the acid include -C (R 36 ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), and -C (R 01 ) (R 02 ). ) (OR 39 ) and the like. In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be coupled to each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
　Ｒ０１及びＲ０２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
　酸分解性基としては好ましくは、第３級アルキルエステル基、アセタールエステル基、クミルエステル基、エノールエステル基等である。更に好ましくは、第３級アルキルエステル基、アセタールエステル基であり、これを用いることにより高感度で高解像性の感光膜が得られる。 The acid-degradable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group or the like. More preferably, it is a tertiary alkyl ester group or an acetal ester group, and by using this, a photosensitive film having high sensitivity and high resolution can be obtained.
　酸分解性基としての第３級アルキルエステル基としては、カルボキシ基の水素原子が下記式（ＡＩ）で表される基で置換されたエステル基であることが好ましい。 The tertiary alkyl ester group as the acid-degradable group is preferably an ester group in which the hydrogen atom of the carboxy group is substituted with a group represented by the following formula (AI).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ＡＩ）に於いて、
　Ｔは、単結合又は＊－Ｒｔ－ＣＯＯ－＃（＊は式（ＡＩ）中の＊と同義であり、＃はＲｘ１～Ｒｘ３と結合する炭素原子との結合部位を表す）を表す。Ｒｔは、アルキレン基又はシクロアルキレン基を表す。
　Ｒｘ１～Ｒｘ３は、それぞれ独立に、水素原子、アルキル基（直鎖若しくは分岐）又はシクロアルキル基（単環若しくは多環）を表す。
　Ｒｘ１～Ｒｘ３の２つが結合して、シクロアルキル基（単環若しくは多環）を形成してもよい。
　＊は他の構造との結合部位を表す。 In the formula (AI)
T represents a single bond or * -Rt-COO- # (* is synonymous with * in the formula (AI), and # represents a binding site with a carbon atom bonded to Rx 1 to Rx 3 ). Rt represents an alkylene group or a cycloalkylene group.
Rx 1 to Rx 3 independently represent a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx 1 to Rx 3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).
* Represents a binding site with another structure.
　Ｒｔは、炭素数１～５のアルキレン基が好ましく、－ＣＨ２－基、－（ＣＨ２）２－基、－（ＣＨ２）３－基がより好ましい。
　Ｒｘ１～Ｒｘ３が表すアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ヘキシル基、オクチル基、ドデシル基などの炭素数１～２０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。 As Rt, an alkylene group having 1 to 5 carbon atoms is preferable, and −CH 2 -group, − (CH 2 ) 2 -group, and − (CH 2 ) 3 -group are more preferable.
Alkyl groups represented by Rx 1 to Rx 3 include carbons such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group, octyl group and dodecyl group. An alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
　Ｒｘ１～Ｒｘ３が表すシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数５又は６の単環のシクロアルキル基が特に好ましい。
　式（ＡＩ）において、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 Examples of the cycloalkyl group represented by Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cyclo such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Alkyl groups are preferred.
Examples of the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl. Polycyclic cycloalkyl groups such as groups are preferred. A monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferable.
In the formula (AI), it is preferable that Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
　上記各基は、置換基を有していてもよく、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、ヒドロキシ基、アルコキシ基（炭素数１～４）、ポリアルキレンオキシ基、カルボキシ基、アルコキシカルボニル基（炭素数２～６）などが挙げられ、炭素数２０以下が好ましい。 Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (1 to 4 carbon atoms), and a polyalkylene group. Examples thereof include an oxy group, a carboxy group and an alkoxycarbonyl group (2 to 6 carbon atoms), and a carbon number of 20 or less is preferable.
　酸分解性基としての第３級アルキルエステル基を構成する式（ＡＩ）で表される基の具体例を以下に示すが、本発明は、これに限定されるものではない。 Specific examples of the group represented by the formula (AI) constituting the tertiary alkyl ester group as the acid-decomposable group are shown below, but the present invention is not limited thereto.
　具体例中、Ｒｘａ、Ｒｘｂはそれぞれ炭素数１～６のアルキル基を表す。Ｚは、上記各基が有していてよい置換基を表し、複数存在する場合は各々独立である。ｐは０又は正の整数を表す。＊は他の構造との結合部位を表す。 In the specific example, Rxa and Rxb each represent an alkyl group having 1 to 6 carbon atoms. Z represents a substituent that each of the above groups may have, and when a plurality of these groups are present, they are independent of each other. p represents 0 or a positive integer. * Represents a binding site with another structure.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　酸分解性基としての第３級アルキルエステル基は、式（ＡＩ）で表される基として、下記式（Ｉ）で表される基及び下記式（ＩＩ）で表される基の少なくともいずれかを有する第３級アルキルエステル基であることがより好ましい。 The tertiary alkyl ester group as an acid-degradable group is, as a group represented by the formula (AI), at least one of a group represented by the following formula (I) and a group represented by the following formula (II). It is more preferable that it is a tertiary alkyl ester group having.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（Ｉ）及び（ＩＩ）中、Ｒ２、Ｒ４、Ｒ５、Ｒ６は、各々独立して、アルキル基又はシクロアルキル基を表す。
　Ｒは、炭素原子とともに脂環構造を形成するのに必要な原子団を表す。
　＊は他の構造との結合部位を表す。 In formulas (I) and (II), R 2 , R 4 , R 5 , and R 6 each independently represent an alkyl group or a cycloalkyl group.
R represents an atomic group required to form an alicyclic structure together with a carbon atom.
* Represents a binding site with another structure.
　Ｒ２におけるアルキル基は、直鎖型でも分岐型でもよく、置換基を有していてもよい。
　Ｒ２におけるシクロアルキル基は、単環でも多環でもよく、置換基を有していてもよい。
　Ｒ２は好ましくはアルキル基であり、より好ましくは炭素数１～１０、更に好ましくは炭素数１～５のものであり、例えばメチル基、エチル基が挙げられる。 The alkyl group in R2 may be a linear type or a branched type, and may have a substituent.
The cycloalkyl group in R2 may be monocyclic or polycyclic, and may have a substituent.
R2 is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.
　Ｒは、炭素原子とともに脂環構造を形成するのに必要な原子団を表す。Ｒが形成する脂環構造としては、単環の脂環構造であることが好ましく、炭化水素環構造であることがより好ましい。上記単環の脂環構造又は炭化水素環構造の炭素数は好ましくは３～８、より好ましくは５又は６である。 R represents an atomic group required to form an alicyclic structure together with carbon atoms. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and more preferably a hydrocarbon ring structure. The alicyclic structure or the hydrocarbon ring structure of the single ring preferably has 3 to 8 carbon atoms, and more preferably 5 or 6 carbon atoms.
　Ｒ４、Ｒ５、Ｒ６におけるアルキル基は、直鎖型でも分岐型でもよく、置換基を有していてもよい。アルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ヘキシル基などの炭素数１～６のものが好ましい。 The alkyl group in R 4 , R 5 and R 6 may be a linear type or a branched type, and may have a substituent. The alkyl group preferably has 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and a hexyl group.
　Ｒ４、Ｒ５、Ｒ６におけるシクロアルキル基は、単環でも多環でもよく、置換基を有していてもよい。シクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。 The cycloalkyl group in R 4 , R 5 , and R 6 may be monocyclic or polycyclic, and may have a substituent. As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group is preferable.
　式（Ｉ）により表される基としては、例えば、下記式（Ｉ－ａ）及び（Ｉ－ｂ）により表される基が挙げられる。 Examples of the group represented by the formula (I) include the groups represented by the following formulas (Ia) and (Ib).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式中、Ｒ２は、式（Ｉ）におけるＲ２と同義である。
　＊は他の構造との結合部位を表す。 In the formula, R 2 is synonymous with R 2 in the formula (I).
* Represents a binding site with another structure.
　式（ＩＩ）で表される基が、下記式（ＩＩ－ａ）で表される基であることが好ましい。 It is preferable that the group represented by the formula (II) is a group represented by the following formula (II-a).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（ＩＩ－ａ）中、
　Ｒ４及びＲ５は、式（ＩＩ）におけるものと同義である。
　＊は他の構造との結合部位を表す。 In formula (II-a),
R4 and R5 are synonymous with those in formula ( II).
* Represents a binding site with another structure.
　酸分解性基としてのアセタールエステル基としては、具体的にはカルボキシ基の水素原子が下記式（ＩＩＩ）で表される基で置換されたエステル基であることが好ましい。 The acetal ester group as the acid-degradable group is preferably an ester group in which the hydrogen atom of the carboxy group is substituted with the group represented by the following formula (III).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　Ｒａは、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。
　Ｒｂは、単結合又は２価の連結基を表す。
　Ｑは、アルキル基、ヘテロ原子を含んでいてもよい脂環基、又は、ヘテロ原子を含んでいてもよい芳香環基を表す。
　Ｒａ、Ｒｂ及びＱの少なくとも２つは、互いに結合して環を形成していてもよい。この環は、５員環又は６員環であることが好ましい。
　＊は他の構造との結合部位を表す。 Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Rb represents a single bond or a divalent linking group.
Q represents an alkyl group, an alicyclic group which may contain a heteroatom, or an aromatic ring group which may contain a heteroatom.
At least two of Ra, Rb and Q may be coupled to each other to form a ring. This ring is preferably a 5-membered ring or a 6-membered ring.
* Represents a binding site with another structure.
　Ｒａとしてのアルキル基、シクロアルキル基、アリール基又はアラルキル基は上記Ｒ３６についてのアルキル基、シクロアルキル基、アリール基、アラルキル基として上述したものと同様のものが挙げられる。
　保存中の酸分解性基としてのアセタールエステル基の分解を立体障害により抑制でき、パターニング性の低下を防ぐ観点から、Ｒａが下記式（ＩＶ）又は（Ｖ）で表される基であることも好ましい。 Examples of the alkyl group, cycloalkyl group, aryl group or aralkyl group as Ra include the same as the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group for R36.
Ra may be a group represented by the following formula (IV) or (V) from the viewpoint that decomposition of the acetal ester group as an acid-decomposable group during storage can be suppressed by steric hindrance and deterioration of patterning property is prevented. preferable.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記式中、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ及びＲｇは、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、シアノ基又はハロゲン原子を表し、Ｒｃ、Ｒｄが互いに結合して環を形成していてもよく、Ｒｅ、Ｒｆ及びＲｇの少なくとも２つが互いに結合して環を形成していてもよい。
　＊は他の構造との結合部位を表す。
　Ｒａが式（ＩＶ）又は式（Ｖ）で表される基であると、式（１）で表される繰返し単位を有する樹脂において、保存中のイミド化反応の進行を抑制でき、パターニング性の低下を防ぐことができる。
　Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇとしてのアルキル基、シクロアルキル基、アリール基、又は、アラルキル基は上記Ｒ３６についてのアルキル基、シクロアルキル基、アリール基、アラルキル基として上述したものと同様のものが挙げられる。
　Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇとしてのアルコキシ基としては、炭素数１～２０のアルコキシ基が好ましく、炭素数１～６のアルコキシ基がより好ましい。
　また、上記アルコキシ基におけるアルキル基部は直鎖状、分岐鎖状又は環状のいずれであってもよく、これらを組み合わせた態様であってもよい。
　Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇとしてのアリールオキシ基としては、炭素数６～１０のアリールオキシ基が好ましく、具体的にはフェノキシ、トルイルオキシ、１－ナフトキシ等が挙げられる。
　Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇとしてのアルコキシカルボニル基としては、炭素数１～１０のアルコキシカルボニル基が好ましく、具体的にはメトキシカルボニル、エトキシカルボニル、直鎖又は分岐プロポキシカルボニル、シクロペンチルオキシカルボニル、シクロヘキシルオキシカルボニル等が挙げられる。
　Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇとしてのアリールオキシカルボニル基のアリールオキシ部分としては、上述のアリールオキシ基と同様のものが挙げられる。 In the above formula, Rc, Rd, Re, Rf and Rg are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group and a cyano group. Alternatively, it represents a halogen atom, and Rc and Rd may be bonded to each other to form a ring, or at least two of Re, Rf and Rg may be bonded to each other to form a ring.
* Represents a binding site with another structure.
When Ra is a group represented by the formula (IV) or the formula (V), the progress of the imidization reaction during storage can be suppressed in the resin having the repeating unit represented by the formula (1), and the patterning property can be improved. It is possible to prevent the decrease.
The alkyl group, cycloalkyl group, aryl group, or aralkyl group as Rc, Rd, Re, Rf, Rg is the same as the above-mentioned alkyl group, cycloalkyl group, aryl group, aralkyl group for R36. Things can be mentioned.
As the alkoxy group as Rc, Rd, Re, Rf, Rg, an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl base portion of the alkoxy group may be linear, branched or cyclic, or may be a combination thereof.
As the aryloxy group as Rc, Rd, Re, Rf and Rg, an aryloxy group having 6 to 10 carbon atoms is preferable, and specific examples thereof include phenoxy, toluyloxy and 1-naphthoxy.
As the alkoxycarbonyl group as Rc, Rd, Re, Rf, Rg, an alkoxycarbonyl group having 1 to 10 carbon atoms is preferable, and specifically, methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, Cyclohexyloxycarbonyl and the like can be mentioned.
Examples of the aryloxy moiety of the aryloxycarbonyl group as Rc, Rd, Re, Rf and Rg include those similar to the above-mentioned aryloxy group.
　保存中の酸分解性基としてのアセタールエステル基の分解を抑制でき、パターニング性の低下を防ぐ観点から、式（ＩＶ）におけるＲｃ、Ｒｄの少なくとも１つが、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、シアノ基、又は、ハロゲン原子であることが好ましく、少なくとも１つが、アリール基であることがより好ましい。 From the viewpoint of suppressing the decomposition of the acetal ester group as an acid-degradable group during storage and preventing the deterioration of the patterning property, at least one of Rc and Rd in the formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, and the like. It is preferably an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and more preferably at least one is an aryl group.
　Ｒｂとしての２価の連結基は、例えば、アルキレン基（好ましくは炭素数１～８のアルキレン基、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基又はオクチレン基）、シクロアルキレン基（好ましくは炭素数３～１５のシクロアルキレン基、例えば、シクロペンチレン基又はシクロヘキシレン基）、－Ｓ－、－Ｏ－、－ＣＯ－、－ＣＳ－、－ＳＯ２－、－Ｎ（Ｒ０）－、又はこれらの２種以上の組み合わせであり、総炭素数が２０以下のものが好ましい。ここで、Ｒ０は、水素原子又はアルキル基（例えば炭素数１～８のアルキル基であって、具体的には、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基及びオクチル基等）である。
　Ｒｂは、単結合、アルキレン基、又はアルキレン基と－Ｏ－、－ＣＯ－、－ＣＳ－及び－Ｎ（Ｒ０）－の少なくとも一つとの組み合わせからなる２価の連結基が好ましく、単結合、アルキレン基、又はアルキレン基と－Ｏ－との組み合わせからなる２価の連結基がより好ましい。ここで、Ｒ０は上述のＲ０と同義である。 The divalent linking group as Rb is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group. (Preferably a cycloalkylene group having 3 to 15 carbon atoms, for example, a cyclopentylene group or a cyclohexylene group), -S-, -O-, -CO-, -CS-, -SO 2- , -N (R). 0 )-Or a combination of two or more of these, preferably having a total carbon number of 20 or less. Here, R 0 is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and the like. Hexyl group, octyl group, etc.).
Rb is preferably a single bond, an alkylene group, or a divalent linking group consisting of a combination of an alkylene group and at least one of -O-, -CO-, -CS- and -N (R 0 )-, and a single bond is preferable. , An alkylene group, or a divalent linking group consisting of a combination of an alkylene group and —O— is more preferred. Here, R 0 is synonymous with the above-mentioned R 0 .
　Ｑとしてのアルキル基は、例えば、上述したＲａとしてのアルキル基と同様である。 The alkyl group as Q is, for example, the same as the above-mentioned alkyl group as Ra.
　Ｑとしての脂環基及び芳香環基としては、例えば、上述したＲａとしてのシクロアルキル基及びアリール基が挙げられる。その炭素数は、好ましくは、３～１８である。なお、本発明においては、複数の芳香環が単結合を介して連結されてなる基（例えば、ビフェニル基、ターフェニル基）もＱとしての芳香族基に含まれる。
　ヘテロ原子を含む脂環基及びヘテロ原子を含む芳香環基としては、例えば、チイラン、シクロチオラン、チオフェン、フラン、ピロール、ベンゾチオフェン、ベンゾフラン、ベンゾピロール、トリアジン、イミダゾール、ベンゾイミダゾール、トリアゾール、チアジアゾール、チアゾール及びピロリドンが挙げられる。
　Ｑとしての脂環基及び芳香環基は、置換基を有していてもよく、例えば、アルキル基、シクロアルキル基、シアノ基、ハロゲン原子、ヒドロキシ基、アルコキシ基、カルボキシ基、アルコキシカルボニル基が挙げられる。 Examples of the alicyclic group and aromatic ring group as Q include the cycloalkyl group and aryl group as Ra described above. Its carbon number is preferably 3 to 18. In the present invention, a group in which a plurality of aromatic rings are linked via a single bond (for example, a biphenyl group and a terphenyl group) is also included in the aromatic group as Q.
Examples of the alicyclic group containing a heteroatom and the aromatic ring group containing a heteroatom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole and thiazole. And pyrrolidone.
The alicyclic group and the aromatic ring group as Q may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group and an alkoxycarbonyl group. Can be mentioned.
　（－Ｒｂ－Ｑ）として特に好ましくは、メチル基、アリールオキシエチル基、シクロヘキシルエチル基若しくはアリールエチル基であり、溶解性、熱安定性が向上する。 Particularly preferred as (-Rb-Q) is a methyl group, an aryloxyethyl group, a cyclohexylethyl group or an arylethyl group, which improves solubility and thermal stability.
　Ｒａ、Ｒｂ及びＱの少なくとも２つが互いに結合して環を形成する場合としては、例えば、Ｒｂ及びＱのいずれかとＲａとが結合してプロピレン基又はブチレン基を形成して、酸素原子を含有する５員環又は６員環を形成する場合が挙げられる。 When at least two of Ra, Rb and Q are bonded to each other to form a ring, for example, any of Rb and Q and Ra are bonded to form a propylene group or a butylene group and contain an oxygen atom. The case of forming a 5-membered ring or a 6-membered ring may be mentioned.
　Ｒａ、Ｒｂ及びＱの炭素数の総和をＮＣと表記すると、ＮＣが大きい場合には式（ＩＩＩ）で表される基が脱離する前後の、樹脂のアルカリ溶解速度変化が大きくなり、溶解コントラストが硬調化して解像性が向上する。ＮＣの範囲としては、好ましくは２～２０であり、２～１５が特に好ましい。ＮＣが２０以下であると、高分子化合物のガラス転移温度が低下することが抑制され、更に酸分解性基からの脱離物がパターン上に付着する欠陥の生成が抑制される。 When the total number of carbon atoms of Ra, Rb and Q is expressed as NC, when NC is large, the change in the alkali dissolution rate of the resin becomes large before and after the group represented by the formula (III) is eliminated. The dissolution contrast becomes hard and the resolution is improved. The range of NC is preferably 2 to 20, and particularly preferably 2 to 15. When NC is 20 or less, the decrease in the glass transition temperature of the polymer compound is suppressed, and the formation of defects in which desorbed substances from acid-degradable groups adhere to the pattern is suppressed.
　Ｒａ、Ｒｂ及びＱの少なくとも１つが、電子求引性基ないしは電子求引性基を有する基であることが好ましい。これにより、式（１）で表される繰返し単位を有する樹脂において、保存中の酸分解性基の分解を抑制でき、パターニング性の低下を防ぐことができる。
　電子求引性基としては、例えば、アルコキシ基、アリール基、アルケニル基、アルキニル基、ハロゲン原子、アシル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールオキシ基、ニトリル基（シアノ基）、アルキルスルホニル基、アリールスルホニル基、ニトロ基等が挙げられ、アルコキシ基、アリール基、アシル基であることが好ましい。 It is preferable that at least one of Ra, Rb and Q is an electron-withdrawing group or a group having an electron-withdrawing group. Thereby, in the resin having the repeating unit represented by the formula (1), the decomposition of the acid-decomposable group during storage can be suppressed, and the deterioration of the patterning property can be prevented.
Examples of the electron-attracting group include an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxy group and a nitrile group (cyano group). ), An alkylsulfonyl group, an arylsulfonyl group, a nitro group and the like, and an alkoxy group, an aryl group, an acyl group and the like are preferable.
　以下に、酸分解性基としてのアセタールエステル基を構成する式（ＩＩＩ）で表される基の具体例を示すが、これらに限定されるものではない。＊は他の構造との結合部位を表す。 The following are specific examples of the group represented by the formula (III) constituting the acetal ester group as the acid-degradable group, but the present invention is not limited thereto. * Represents a binding site with another structure.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（１）における－ＣＯ２Ｒ３の熱分解温度が１００～２２０℃であることが好ましく、１２０～２１０℃であることがより好ましく、１４０～２００℃であることが特に好ましい。熱分解温度は、例えば、示差熱天秤分析から求めることができる。
　熱分解温度が上記下限以上であれば、本発明の樹脂組成物の保存安定性が向上する。また、熱分解温度が上記上限以下であれば、本発明の樹脂組成物の露光感度が向上する。 The thermal decomposition temperature of —CO 2 R 3 in the formula (1) is preferably 100 to 220 ° C, more preferably 120 to 210 ° C, and particularly preferably 140 to 200 ° C. The pyrolysis temperature can be determined, for example, from differential thermal balance analysis.
When the thermal decomposition temperature is at least the above lower limit, the storage stability of the resin composition of the present invention is improved. Further, when the thermal decomposition temperature is not more than the above upper limit, the exposure sensitivity of the resin composition of the present invention is improved.
　上述のような熱分解温度を達成し得るＲ３の構造として具体的には、上記式（Ａ１）中のＲｘ１～Ｒｘ３のうち、少なくとも１つが下記式（ＶＩ）で表される基である構造、上記式（ＩＩＩ）中のＲａが上記式（ＩＶ）又は下記式（ＶＩＩ）で表される基である構造などが挙げられる。 Specifically, as the structure of R 3 capable of achieving the above-mentioned thermal decomposition temperature, at least one of Rx 1 to Rx 3 in the above formula (A1) is a group represented by the following formula (VI). Examples thereof include a certain structure, a structure in which Ra in the above formula (III) is a group represented by the above formula (IV) or the following formula (VII).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記式（ＶＩ）中、Ｒ７～Ｒ８は、それぞれ独立に、水素原子、アルキル基（直鎖若しくは分岐）又はシクロアルキル基（単環若しくは多環）を表し、Ｒ７～Ｒ８の少なくとも１つは水素原子である。＊は他の構造との結合部位を表す。 In the above formula (VI), R 7 to R 8 independently represent a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic), and at least R 7 to R 8 are represented. One is a hydrogen atom. * Represents a binding site with another structure.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記式（ＶＩＩ）中、　Ｒｈはアルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、シアノ基又はハロゲン原子を表す。＊は他の構造との結合部位を表す。
　Ｒ７～Ｒ８についてのアルキル基、シクロアルキル基の具体例、好ましい例としては、Ｒｘ１～Ｒｘ３についてのアルキル基、シクロアルキル基として上述した具体例、好ましい例と同様のものが挙げられる。
　Ｒｈとしてのアルキル基、シクロアルキル基、アリール基、アラルキル基又はアルコキシ基は上記Ｒ３６についてのアルキル基、シクロアルキル基、アリール基、アラルキル基として上述したものと同様のものが挙げられる。
　Ｒｈとしてのアルコキシ基としては、炭素数１～２０のアルコキシ基が好ましく、炭素数１～６のアルコキシ基がより好ましい。
　また、上記アルコキシ基におけるアルキル基部は直鎖状、分岐鎖状又は環状のいずれであってもよく、これらを組み合わせた態様であってもよい。
　Ｒｈとしてのアリールオキシ基としては、炭素数６～１０のアリールオキシ基が好ましく、具体的にはフェノキシ、トルイルオキシ、１－ナフトキシ等が挙げられる。
　Ｒｈとしてのアルコキシカルボニル基としては、炭素数１～１０のアルコキシカルボニル基が好ましく、具体的にはメトキシカルボニル、エトキシカルボニル、直鎖又は分岐プロポキシカルボニル、シクロペンチルオキシカルボニル、シクロヘキシルオキシカルボニル等が挙げられる。
　Ｒｈとしてのアリールオキシカルボニル基のアリールオキシ部分としては、上述のアリールオキシ基と同様のものが挙げられる。 In the above formula (VII), Rh represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom. * Represents a binding site with another structure.
Specific examples of the alkyl group and cycloalkyl group for R 7 to R 8 , preferred examples include the alkyl group for Rx 1 to Rx 3 , and the above-mentioned specific examples and preferred examples of the cycloalkyl group. ..
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rh include the same as the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group for R36 .
As the alkoxy group as Rh, an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl base portion of the alkoxy group may be linear, branched or cyclic, or may be a combination thereof.
As the aryloxy group as Rh, an aryloxy group having 6 to 10 carbon atoms is preferable, and specific examples thereof include phenoxy, toluyloxy, 1-naphthoxy and the like.
The alkoxycarbonyl group as Rh is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like.
Examples of the aryloxy moiety of the aryloxycarbonyl group as Rh include the same as the above-mentioned aryloxy group.
　また、式（１）中のＲ３は酸の作用により分解しアルカリ可溶性基を生じる基とは異なる有機基であってもよい。
　このような有機基としては、本発明の効果が得られる範囲内において特に制限なく使用することができるが、直鎖または分岐鎖状のアルキル基、シクロアルキル基、アリール基、又は、ポリアルキレンオキシ基等が挙げられる。これらの基の好ましい態様は、上述のＲ３６におけるこれらの基の好ましい態様と同様である。 Further, R 3 in the formula (1) may be an organic group different from the group which is decomposed by the action of an acid to form an alkali-soluble group.
Such an organic group can be used without particular limitation as long as the effect of the present invention can be obtained, but it may be a linear or branched alkyl group, a cycloalkyl group, an aryl group, or a polyalkyleneoxy. The group etc. can be mentioned. Preferred embodiments of these groups are similar to the preferred embodiments of these groups in R36 described above.
　本発明においては、Ｒ３において水素原子と有機基を混在させることができる。樹脂中の全Ｒ３に対して有機基の割合が１００モル％～２０モル％であることが好ましく、有機基の割合が１００モル％～４０モル％が有機基であることがより好ましい。このＲ３の水素原子と有機基の量を調整することで、アルカリ水溶液に対する溶解速度が変化するので、この調整により適度な溶解速度を有した樹脂組成物を得ることができる。
　樹脂中の全ての－ＣＯ２Ｒ３のうち、酸の作用により分解しアルカリ可溶性基を生じる基が占める割合、いわゆる保護率は、４０～１００％であることが好ましく、４５～１００％であることがより好ましい。
　また、本発明においては、式（１）で表される繰返し単位を主成分とするポリマーの末端に末端封止剤を反応させることができる。末端封止剤は、モノアルコール、フェノール、チオール、チオフェノール、モノアミン、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などを用いることができる。末端封止剤を反応させることにより、繰返し単位の繰返し数、すなわち分子量を好ましい範囲に制御できる点で好ましい。更に、末端封止剤により、末端アミンと発生酸の中和による酸失活を抑制する事ができる。また、末端に末端封止剤を反応させることにより、末端基として種々の有機基、例えば炭素－炭素不飽和結合を有する架橋反応性基を導入することができる。 In the present invention, a hydrogen atom and an organic group can be mixed in R3. The ratio of the organic group to the total R 3 in the resin is preferably 100 mol% to 20 mol%, and the ratio of the organic group is more preferably 100 mol% to 40 mol%. By adjusting the amounts of hydrogen atoms and organic groups of R3 , the dissolution rate in an alkaline aqueous solution changes, and this adjustment makes it possible to obtain a resin composition having an appropriate dissolution rate.
Of all -CO 2 R 3 in the resin, the ratio of the groups decomposed by the action of an acid to produce an alkali-soluble group, the so-called protection rate, is preferably 40 to 100%, preferably 45 to 100%. Is more preferable.
Further, in the present invention, the terminal encapsulant can be reacted with the end of the polymer containing the repeating unit represented by the formula (1) as a main component. As the terminal encapsulant, monoalcohol, phenol, thiol, thiophenol, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. By reacting the terminal encapsulant, the number of repetitions of the repetition unit, that is, the molecular weight can be controlled within a preferable range, which is preferable. Further, the terminal encapsulant can suppress acid deactivation due to neutralization of the terminal amine and the generated acid. Further, by reacting the terminal with an end-capping agent, various organic groups such as a cross-linking reactive group having a carbon-carbon unsaturated bond can be introduced as the terminal group.
　末端封止剤に用いられるモノアルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、ドデシノール、ベンジルアルコール、２－フェニルエタノール、２－メトキシエタノール、２－クロロメタノール、フルフリルアルコール等の１級アルコール、イソプロパノール、２－ブタノール、シクロヘキシルアルコール、シクロペンタノール、１－メトキシ－２－プロパノール等の２級アルコール、ｔ－ブチルアルコール、アダマンタンアルコール等の３級アルコールが挙げられる。フェノール類の好ましい化合物としては、フェノール、メトキシフェノール、メチルフェノール、ナフタレン－１－オール、ナフタレン－２－オール、ヒドロキシスチレン等のフェノール類などが挙げられる。 Examples of the monoalcohol used for the terminal encapsulant include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol and the like. Examples thereof include secondary alcohols such as class alcohols, isopropanols, 2-butanols, cyclohexyl alcohols, cyclopentanols and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohols and adamantan alcohols. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
　末端封止剤に用いられるモノアミンは、５－アミノ－８－ヒドロキシキノリン、４－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－８－アミノナフタレン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、１－ヒドロキシ－３－アミノナフタレン、１－ヒドロキシ－２－アミノナフタレン、１－アミノ－７－ヒドロキシナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、２－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－３－アミノナフタレン、１－アミノ－２－ヒドロキシナフタレン、１－カルボキシ－８－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、１－カルボキシ－４－アミノナフタレン、１－カルボキシ－３－アミノナフタレン、１－カルボキシ－２－アミノナフタレン、１－アミノ－７－カルボキシナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－カルボキシ－４－アミノナフタレン、２－カルボキシ－３－アミノナフタレン、１－アミノ－２－カルボキシナフタレン、２－アミノニコチン酸、４－アミノニコチン酸、５－アミノニコチン酸、６－アミノニコチン酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、３－アミノ－Ｏ－トルイック酸、アメライド、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、５－アミノ－８－メルカプトキノリン、４－アミノ－８－メルカプトキノリン、１－メルカプト－８－アミノナフタレン、１－メルカプト－７－アミノナフタレン、１－メルカプト－６－アミノナフタレン、１－メルカプト－５－アミノナフタレン、１－メルカプト－４－アミノナフタレン、１－メルカプト－３－アミノナフタレン、１－メルカプト－２－アミノナフタレン、１－アミノ－７－メルカプトナフタレン、２－メルカプト－７－アミノナフタレン、２－メルカプト－６－アミノナフタレン、２－メルカプト－５－アミノナフタレン、２－メルカプト－４－アミノナフタレン、２－メルカプト－３－アミノナフタレン、１－アミノ－２－メルカプトナフタレン、３－アミノ－４，６－ジメルカプトピリミジン、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノール、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、２，４－ジエチニルアニリン、２，５－ジエチニルアニリン、２，６－ジエチニルアニリン、３，４－ジエチニルアニリン、３，５－ジエチニルアニリン、１－エチニル－２－アミノナフタレン、１－エチニル－３－アミノナフタレン、１－エチニル－４－アミノナフタレン、１－エチニル－５－アミノナフタレン、１－エチニル－６－アミノナフタレン、１－エチニル－７－アミノナフタレン、１－エチニル－８－アミノナフタレン、２－エチニル－１－アミノナフタレン、２－エチニル－３－アミノナフタレン、２－エチニル－４－アミノナフタレン、２－エチニル－５－アミノナフタレン、２－エチニル－６－アミノナフタレン、２－エチニル－７－アミノナフタレン、２－エチニル－８－アミノナフタレン、３，５－ジエチニル－１－アミノナフタレン、３，５－ジエチニル－２－アミノナフタレン、３，６－ジエチニル－１－アミノナフタレン、３，６－ジエチニル－２－アミノナフタレン、３，７－ジエチニル－１－アミノナフタレン、３，７－ジエチニル－２－アミノナフタレン、４，８－ジエチニル－１－アミノナフタレン、４，８－ジエチニル－２－アミノナフタレン、アニリン等が挙げられるが、これらに限定されるものではない。 The monoamines used in the terminal encapsulants are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-. 6-Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1 -Carbox-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5- Aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6- Aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, ameride, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8 -Mercaptoquinolin, 4-amino-8-mercaptoquinolin, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1 -Mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthal Len, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino -2-Mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline , 2,4-dietinylaniline, 2,5-dietinylaniline, 2,6-dietinylaniline, 3,4-dietinylaniline, 3,5-dietinylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8 -Aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2 -Ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-dietinyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-dietinyl-2-aminonaphthalene, 3,7-dietinyl-1-aminonaphthalene, 3,7-dietinyl-2-aminonaphthalene, 4,8-dietinyl-1-aminonaphthalene, 4,8-dietinyl- Examples thereof include, but are not limited to, 2-aminonaphthalene and aniline.
　これらのうち、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノール、３－エチニルアニリン、４－エチニルアニリン、３，４－ジエチニルアニリン、３，５－ジエチニルアニリン、アニリン等が好ましい。 Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-Aminophenol, 4-Aminophenol, 2-Aminothiophenol, 3-Aminothiophenol, 4-Aminothiophenol, 3-Etinylaniline, 4-Etinylaniline, 3,4-diethynylaniline, 3,5- Diethynylaniline, aniline and the like are preferable.
　末端封止剤として用いられる酸無水物、モノカルボン酸、モノ酸クロリド化合物、活性エステル化合物は、無水フタル酸、無水マレイン酸、無水ナジック酸、シクロヘキサンジカルボン酸無水物、３－ヒドロキシフタル酸無水物等の酸無水物、２－カルボキシフェノール、３－カルボキシフェノール、４－カルボキシフェノール、２－カルボキシチオフェノール、３－カルボキシチオフェノール、４－カルボキシチオフェノール、１－ヒドロキシ－８－カルボキシナフタレン、１－ヒドロキシ－７－カルボキシナフタレン、１－ヒドロキシ－６－カルボキシナフタレン、１－ヒドロキシ－５－カルボキシナフタレン、１－ヒドロキシ－４－カルボキシナフタレン、１－ヒドロキシ－３－カルボキシナフタレン、１－ヒドロキシ－２－カルボキシナフタレン、１－メルカプト－８－カルボキシナフタレン、１－メルカプト－７－カルボキシナフタレン、１－メルカプト－６－カルボキシナフタレン、１－メルカプト－５－カルボキシナフタレン、１－メルカプト－４－カルボキシナフタレン、１－メルカプト－３－カルボキシナフタレン、１－メルカプト－２－カルボキシナフタレン、２－カルボキシベンゼンスルホン酸、３－カルボキシベンゼンスルホン酸、４－カルボキシベンゼンスルホン酸、２－エチニル安息香酸、３－エチニル安息香酸、４－エチニル安息香酸、２，４－ジエチニル安息香酸、２，５－ジエチニル安息香酸、２，６－ジエチニル安息香酸、３，４－ジエチニル安息香酸、３，５－ジエチニル安息香酸、２－エチニル－１－ナフトエ酸、３－エチニル－１－ナフトエ酸、４－エチニル－１－ナフトエ酸、５－エチニル－１－ナフトエ酸、６－エチニル－１－ナフトエ酸、７－エチニル－１－ナフトエ酸、８－エチニル－１－ナフトエ酸、２－エチニル－２－ナフトエ酸、３－エチニル－２－ナフトエ酸、４－エチニル－２－ナフトエ酸、５－エチニル－２－ナフトエ酸、６－エチニル－２－ナフトエ酸、７－エチニル－２－ナフトエ酸、８－エチニル－２－ナフトエ酸等のモノカルボン酸類及びこれらのカルボキシ基が酸クロリド化したモノ酸クロリド化合物、及びテレフタル酸、フタル酸、マレイン酸、シクロヘキサンジカルボン酸、３－ヒドロキシフタル酸、５－ノルボルネン－２，３－ジカルボン酸、１，２－ジカルボキシナフタレン、１，３－ジカルボキシナフタレン、１，４－ジカルボキシナフタレン、１，５－ジカルボキシナフタレン、１，６－ジカルボキシナフタレン、１，７－ジカルボキシナフタレン、１，８－ジカルボキシナフタレン、２，３－ジカルボキシナフタレン、２，６－ジカルボキシナフタレン、２，７－ジカルボキシナフタレン等のジカルボン酸類のモノカルボキシ基だけが酸クロリド化したモノ酸クロリド化合物、モノ酸クロリド化合物とＮ－ヒドロキシベンゾトリアゾールやＮ－ヒドロキシ－５－ノルボルネン－２，３－ジカルボキシイミドとの反応により得られる活性エステル化合物等が挙げられる。 Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as terminal encapsulants are phthalic acid anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxylene Naphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto -3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4- Ethynyl benzoic acid, 2,4-dietinyl benzoic acid, 2,5-dietinyl benzoic acid, 2,6-dietinyl benzoic acid, 3,4-dietinyl benzoic acid, 3,5-dietinyl benzoic acid, 2-ethynyl-1- Nafteic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8- Ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid Monocarboxylic acids such as acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxy groups are acid chlorides, and terephthalic acid, phthalic acid, maleic acid, cyclohexane. Dicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornen-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboki Cinaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene , A monoacid chloride compound in which only the monocarboxy group of dicarboxylic acids such as 2,7-dicarboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples thereof include active ester compounds obtained by reaction with dicarboxyimide.
　これらのうち、無水フタル酸、無水マレイン酸、無水ナジック酸、シクロヘキサンジカルボン酸無水物、３－ヒドロキシフタル酸無水物等の酸無水物、３－カルボキシフェノール、４－カルボキシフェノール、３－カルボキシチオフェノール、４－カルボキシチオフェノール、１－ヒドロキシ－７－カルボキシナフタレン、１－ヒドロキシ－６－カルボキシナフタレン、１－ヒドロキシ－５－カルボキシナフタレン、１－メルカプト－７－カルボキシナフタレン、１－メルカプト－６－カルボキシナフタレン、１－メルカプト－５－カルボキシナフタレン、３－カルボキシベンゼンスルホン酸、４－カルボキシベンゼンスルホン酸、３－エチニル安息香酸、４－エチニル安息香酸、３，４－ジエチニル安息香酸、３，５－ジエチニル安息香酸等のモノカルボン酸類、及びこれらのカルボキシ基が酸クロリド化したモノ酸クロリド化合物、テレフタル酸、フタル酸、マレイン酸、シクロヘキサンジカルボン酸、１，５－ジカルボキシナフタレン、１，６－ジカルボキシナフタレン、１，７－ジカルボキシナフタレン、２，６－ジカルボキシナフタレン等のジカルボン酸類のモノカルボキシ基だけが酸クロリド化したモノ酸クロリド化合物、モノ酸クロリド化合物とＮ－ヒドロキシベンゾトリアゾールやＮ－ヒドロキシ－５－ノルボルネン－２，３－ジカルボキシイミドとの反応により得られる活性エステル化合物等が好ましい。 Among these, acid anhydrides such as phthalic acid anhydride, maleic acid anhydride, nagic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol , 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-dietinylbenzoic acid, 3,5-diethynyl Monocarboxylic acids such as benzoic acid, monoacid chloride compounds in which these carboxy groups are acid chlorides, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxyne. Monoacid chloride compounds in which only the monocarboxy group of dicarboxylic acids such as naphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene are acid chlorides, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy An active ester compound obtained by reaction with -5-norbornen-2,3-dicarboxyimide is preferable.
　末端封止剤に用いられるモノアミンの導入割合は、全アミン成分に対して、０．１～６０モル％の範囲が好ましく、特に好ましくは５～５０モル％である。末端封止剤として用いられる酸無水物、モノカルボン酸、モノ酸クロリド化合物及びモノ活性エステル化合物から選ばれた化合物の導入割合は、ジアミン成分に対して、０．１～１００モル％の範囲が好ましく、特に好ましくは５～９０モル％である。複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 The introduction ratio of the monoamine used in the terminal encapsulant is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol% with respect to the total amine component. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the terminal encapsulant is in the range of 0.1 to 100 mol% with respect to the diamine component. It is preferable, and particularly preferably 5 to 90 mol%. A plurality of different end groups may be introduced by reacting a plurality of end sealants.
　ポリマー中に導入された末端封止剤は、以下の方法で容易に検出できる。例えば、末端封止剤が導入されたポリマーを酸性溶液に溶解し、ポリマーの構成単位であるアミン成分と酸無水物成分に分解する。これをガスクロマトグラフィー（ＧＣ）や、ＮＭＲ測定することにより、末端封止剤を容易に検出できる。その他に、末端封止剤が導入されたポリマー成分を直接、熱分解ガスクロマトグラフ（ＰＧＣ）や赤外スペクトル及び１３ＣＮＭＲスペクトル測定することによっても、容易に検出可能である。 The terminal sealant introduced into the polymer can be easily detected by the following method. For example, the polymer into which the terminal encapsulant has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer. By gas chromatography (GC) or NMR measurement of this, the terminal encapsulant can be easily detected. In addition, the polymer component into which the terminal encapsulant has been introduced can be easily detected by directly measuring the pyrolysis gas chromatograph (PGC), the infrared spectrum, and the 13 CNMR spectrum.
　本発明の樹脂組成物に用いられる特定樹脂は、式（１）で表される繰返し単位を主成分とするものであることが好ましい。ここでいう主成分とは、式（１）で表される繰返し単位を７０モル％以上含有していることを意味する。より好ましくは８０モル％以上、最も好ましくは９０モル％以上である。
　本発明に用いられる特定樹脂は、式（１）で表される繰返し単位と他の繰返し単位との共重合体であっても、あるいは、式（１）で表される繰返し単位を含有する複数の樹脂の混合物であってもよい。
　さらには、式（１）で表される繰返し単位を含有する樹脂と式（１）で表される繰返し単位を含有しない樹脂（例えば、式（１）において、Ｒ３に酸の作用により分解しアルカリ可溶性基を生じる基を有しない樹脂）との混合物であってもよい。この場合、式（１）で表される繰返し単位を含有する樹脂は、５０質量％以上含有することが好ましく、７５質量％以上含有することがより好ましい。
　共重合あるいは混合に用いられる繰返し単位の種類及び量は、最終加熱処理によって得られるポリマーの耐熱性を損なわない範囲で選択することが好ましい。 The specific resin used in the resin composition of the present invention preferably contains a repeating unit represented by the formula (1) as a main component. The main component referred to here means that it contains 70 mol% or more of the repeating unit represented by the formula (1). It is more preferably 80 mol% or more, and most preferably 90 mol% or more.
The specific resin used in the present invention may be a copolymer of a repeating unit represented by the formula (1) and another repeating unit, or may contain a plurality of repeating units represented by the formula (1). It may be a mixture of the resins of.
Furthermore, the resin containing the repeating unit represented by the formula (1) and the resin not containing the repeating unit represented by the formula (1) (for example, in the formula (1) , are decomposed into R3 by the action of an acid. It may be a mixture with a resin that does not have a group that produces an alkali-soluble group). In this case, the resin containing the repeating unit represented by the formula (1) is preferably contained in an amount of 50% by mass or more, more preferably 75% by mass or more.
The type and amount of the repeating unit used for the copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.
　式（１）で表される繰返し単位を含む樹脂は、アルカリ溶解速度、膜物性等の観点から、質量平均分子量で、２００，０００以下であることが好ましく、１，０００～２００，０００がより好ましく、２，０００～１００，０００が更に好ましく、３，０００～１００，０００が特に好ましい。この分子量範囲とすることにより、応力が低く、機械特性に優れ、更に現像欠陥の少ない解像性に優れた感光膜を得ることが出来る。
　分散度（分子量分布）は、１．０～７．０であることが好ましく、１．５～６．５であることがより好ましい。
　本明細書において、分散度とは、重量平均分子量／数平均分子量により算出される値である。
　また、樹脂組成物が複数種の特定樹脂を含む場合、少なくとも１種の特定樹脂の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種の特定樹脂を１つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The resin containing the repeating unit represented by the formula (1) preferably has a mass average molecular weight of 200,000 or less, preferably 1,000 to 200,000, from the viewpoint of alkali dissolution rate, film physical characteristics, and the like. It is preferable, more preferably 2,000 to 100,000, and particularly preferably 3,000 to 100,000. By setting this molecular weight range, it is possible to obtain a photosensitive film having low stress, excellent mechanical properties, and excellent resolution with few development defects.
The degree of dispersion (molecular weight distribution) is preferably 1.0 to 7.0, more preferably 1.5 to 6.5.
In the present specification, the degree of dispersion is a value calculated by weight average molecular weight / number average molecular weight.
When the resin composition contains a plurality of types of specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one specific resin are within the above ranges. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of specific resins as one resin are each within the above ranges.
　本発明における特定樹脂の製造方法は、従来公知の方法がいずれも用いられてよい（例えば、最新ポリイミド～基礎と応用～（日本ポリイミド研究会編）参照。）。
　例えば、ポリアミド酸又はポリアミド酸エステルの場合低温中でテトラカルボン酸二無水物とジアミン化合物を反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後アミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸を酸クロリド化し、アミンと反応させる方法、側鎖のカルボキシ基の一部を熱処理によってイミド化させたり、エステル化試薬などを用いてアルキルエステル化させたりする方法などがある。
　中でも、有機溶媒中、ジアミン化合物とテトラカルボン酸二無水物とを－２０～５０℃で数分間から数日間反応させることにより、ポリアミド酸を得、次いで塩基性下ハライド類と反応や、酸性下ビニルエーテル類との反応、あるいはジメチルホルムアミドのジアルキルアセタールとの反応よって式（１）で表される繰返し単位を含有する樹脂を得る方法（合成方法１）、また、Ｍａｋｒｏｍｏｌ．Ｃｈｅｍ．，１９４，５１１～５２１（１９９３）に記載されているような酸分解性基を有するジカルボン酸を合成し、次いでジアミンと重縮合させる方法（合成方法２）が、コスト、操作簡便性、性能再現性の面で好ましい。
（合成方法１） As the method for producing the specific resin in the present invention, any conventionally known method may be used (see, for example, the latest polyimide-basics and applications- (edited by the Japan Polyimide Study Group)).
For example, in the case of polyamic acid or polyamic acid ester, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then in the presence of an amine and a condensing agent. A method of reacting, a method of obtaining a diester with tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid and reacting with an amine, a method of imidizing a part of the carboxy group of the side chain by heat treatment, There is a method of performing alkyl esterification using an esterification reagent or the like.
Above all, the diamine compound and the tetracarboxylic acid dianhydride are reacted at −20 to 50 ° C. for several minutes to several days in an organic solvent to obtain polyamic acid, and then the reaction with basic halides or under acidic conditions. A method for obtaining a resin containing a repeating unit represented by the formula (1) by a reaction with vinyl ethers or a reaction with a dialkyl acetal of dimethylformamide (synthesis method 1), and Makromol. Chem. , 194, 511 to 521 (1993), a method of synthesizing a dicarboxylic acid having an acid-degradable group and then polycondensing it with a diamine (synthesis method 2) is cost effective, easy to operate, and reproduces performance. It is preferable in terms of sex.
(Synthesis method 1)
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（合成方法２） (Synthesis method 2)
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　上記スキーム中、Ｒ１、Ｒ２及びＲ３は式（１）におけるものと同義である。
　このポリアミド酸の合成反応に使用できる有機溶媒としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリジノン、１，３－ジメチル－２－イミダゾリジノン等のアミド系溶媒、ベンゼン、アニソール、ジフェニルエーテル、ニトロベンゼン、ベンゾニトリル、ピリジンのような芳香族系溶媒、クロロホルム、ジクロロメタン、１，２－ジクロロエタン、１，１，２，２－テトラクロロエタンのようなハロゲン系溶媒、テトラヒドロフラン、ジオキサン、ジグリムのようなエーテル系溶媒等を例示することができる。中でもアミド系溶媒が好ましく、高分子量の特定樹脂を得ることができる。 In the above scheme, R 1 , R 2 and R 3 are synonymous with those in the formula (1).
Examples of the organic solvent that can be used in this polyamic acid synthesis reaction include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone. Solvents, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, pyridine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples thereof include ether solvents such as tetrahydrofuran, dioxane, and digrim. Of these, an amide-based solvent is preferable, and a specific resin having a high molecular weight can be obtained.
　重合反応に用いる有機溶媒の沸点は５０℃以上が好ましく、より好ましくは１００℃以上であり、特に好ましくは１５０℃以上である。
　反応液中の溶質の濃度は好ましくは１～５０質量％、より好ましくは５～３０質量％、特に好ましくは１０～２０質量％である。 The boiling point of the organic solvent used in the polymerization reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
The concentration of the solute in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.
　特定樹脂を含む樹脂組成物は半導体基板などの基板上に製膜され、樹脂組成物が感光性の場合（上記製膜された膜が感光膜である場合）には続く露光工程及び現像工程によってレリーフパターンを形成させることが出来る。このパターンの加熱処理により、特定樹脂の脱水閉環が生じ、ポリイミド硬化物が得られる。 The resin composition containing the specific resin is formed on a substrate such as a semiconductor substrate, and when the resin composition is photosensitive (when the formed film is a photosensitive film), it is subjected to the subsequent exposure step and development step. A relief pattern can be formed. By the heat treatment of this pattern, dehydration ring closure of the specific resin occurs, and a polyimide cured product is obtained.
　本発明において、特定樹脂は、上記特定樹脂から形成される膜が膜厚２０μｍ当たりｉ線透過率が１％以上であり、５％以上であることが好ましく、１０％以上であることがより好ましく、１０～８０％であることが特に好ましい。この値が１％未満であると、高解像度で、形状の良好なパターンを形成できる感光性樹脂組成物が得られにくい。ｉ線（波長３６５ｎｍの光）の透過率は、分光光度計（例えば日立Ｕ３４１０型、（株）日立製作所製）により測定することができる。 In the present invention, as the specific resin, the film formed from the specific resin has an i-line transmittance of 1% or more, preferably 5% or more, and more preferably 10% or more per 20 μm film thickness. It is particularly preferably 10 to 80%. When this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern having a good shape with high resolution. The transmittance of i-line (light having a wavelength of 365 nm) can be measured by a spectrophotometer (for example, Hitachi U3410 type, manufactured by Hitachi, Ltd.).
　また、上記式（１）にて示される繰返し単位を有するポリアミド酸エステルからイミド閉環して形成されるポリイミド硬化物の残留応力は、３５ＭＰａ以下であることが好ましく、３０ＭＰａ以下であることがより好ましい。
　なお、ポリイミド膜の残留応力は、常温（２５℃）において、薄膜ストレス測定装置（例えば、テンコール社製、ＦＬＸ－２３２０型）により測定することができる。 Further, the residual stress of the polyimide cured product formed by imide ring closure from the polyamic acid ester having the repeating unit represented by the above formula (1) is preferably 35 MPa or less, more preferably 30 MPa or less. ..
The residual stress of the polyimide film can be measured at room temperature (25 ° C.) by a thin film stress measuring device (for example, FLX-2320 type manufactured by Tencor Co., Ltd.).
　これらの特性を満たす上記式（１）にて示される繰返し単位を有する樹脂は、例えば樹脂の合成の際に適切な原料を選択することにより、芳香環π共役長が抑えられ、剛直でかつ直線な主鎖を形成可能な構造を有することになる。
　本発明の樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましく、５０質量％以上であることが一層好ましい。また、本発明の樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、９９．５質量％以下であることが好ましく、９９質量％以下であることがより好ましく、９８質量％以下であることが更に好ましく、９７質量％以下であることが一層好ましく、９５質量％以下であることがより一層好ましい。
　また、本発明において、特定樹脂は、１種で使用してもよいし、複数併用してもよい。 A resin having a repeating unit represented by the above formula (1) satisfying these characteristics is rigid and linear, for example, by selecting an appropriate raw material when synthesizing the resin, the aromatic ring π-conjugated length is suppressed. It will have a structure capable of forming a main chain.
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
Further, in the present invention, the specific resin may be used alone or in combination of two or more.
＜他の樹脂＞
　本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂（以下、単に「他の樹脂」ともいう）とを含んでもよい。
　他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
　例えば、（メタ）アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン（硬化物）が得られる。
　例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が２０，０００以下の重合性基価の高い（例えば、樹脂１ｇにおける重合性基の含有モル量が１×１０－３モル／ｇ以上である）（メタ）アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン（硬化物）の耐溶剤性等を向上させることができる。 <Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
For example, by further adding a (meth) acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable base value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group contained in 1 g of the resin). (1 × 10 -3 mol / g or more) By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
　本発明の樹脂組成物が他の樹脂を含む場合、他の樹脂の含有量は、樹脂組成物の全固形分に対し、０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましく、１質量％以上であることが更に好ましく、２質量％以上であることが一層好ましく、５質量％以上であることがより一層好ましく、１０質量％以上であることが更に一層好ましい。
　また、本発明の樹脂組成物における、他の樹脂の含有量は、樹脂組成物の全固形分に対し、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましく、６０質量％以下であることが一層好ましく、５０質量％以下であることがより一層好ましい。
　また、本発明の樹脂組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、樹脂組成物の全固形分に対し、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましく、１０質量％以下であることが更に好ましく、５質量％以下であることが一層好ましく、１質量％以下であることがより一層好ましい。上記含有量の下限は特に限定されず、０質量％以上であればよい。
　本発明の樹脂組成物は、他の樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
〔光酸発生剤〕
　本発明の樹脂組成物は、光酸発生剤を含む。
　光酸発生剤とは、２００nm～９００nmの光照射により、ブレンステッド酸、及び、ルイス酸の少なくとも一方を発生させる化合物を表す。照射される光は、好ましくは波長３００ｎｍ～４５０nmの光であり、より好ましくは３３０nm～４２０nmの光である。光酸発生剤単独または増感剤との併用において、感光して酸を発生させることが可能な光酸発生剤であることが好ましい。
　発生する酸の例としては、ハロゲン化水素、カルボン酸、スルホン酸、スルフィン酸、チオスルフィン酸、リン酸、リン酸モノエステル、リン酸ジエステル、ホウ素誘導体、リン誘導体、アンチモン誘導体、過酸化ハロゲン、スルホンアミド等が好ましく挙げられる。 [Photoacid generator]
The resin composition of the present invention contains a photoacid generator.
The photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm. It is preferable that the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
Examples of generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.
　本発明の樹脂組成物に用いられる光酸発生剤としては、例えば、キノンジアジド化合物、オキシムスルホネート化合物、有機ハロゲン化化合物、有機ホウ酸塩化合物、ジスルホン化合物、オニウム塩化合物等が挙げられる。
　感度、保存安定性の観点から、有機ハロゲン化合物、オキシムスルホネート化合物、オニウム塩化合物が好ましく、形成する膜の機械特性等から、オキシムエステルが好ましい。 Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.
　キノンジアジド化合物としては、１価または多価のヒドロキシ化合物にキノンジアジドのスルホン酸がエステル結合したもの、１価または多価のアミノ化合物にキノンジアジドのスルホン酸がスルホンアミド結合したもの、ポリヒドロキシポリアミノ化合物にキノンジアジドのスルホン酸がエステル結合および／またはスルホンアミド結合したものなどが挙げられる。これらポリヒドロキシ化合物、ポリアミノ化合物、ポリヒドロキシポリアミノ化合物の全ての官能基がキノンジアジドで置換されていなくてもよいが、平均して官能基全体の４０モル％以上がキノンジアジドで置換されていることが好ましい。このようなキノンジアジド化合物を含有させることで、一般的な紫外線である水銀灯のｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）、ｇ線（波長４３６ｎｍ）に感光する樹脂組成物を得ることができる。 As the quinone diazide compound, a monovalent or polyvalent hydroxy compound with an ester bond of quinone diazide sulfonic acid, a monovalent or polyvalent amino compound with a sulfonate bond of quinone diazide sulfonic acid, and a polyhydroxypolyamino compound with quinone diazide. Examples thereof include those in which the sulfonic acid of the above is ester-bonded and / or sulfonic acid-bonded. All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that 40 mol% or more of all the functional groups are substituted with quinonediazide on average. .. By containing such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray. ..
　ヒドロキシ化合物として具体的には、フェノール、トリヒドロキシベンゾフェノン、４メトキシフェノール、イソプロパノール、オクタノール、t-Buアルコール、シクロヘキサノール、ナフトール、Ｂｉｓ－Ｚ、ＢｉｓＰ－ＥＺ、ＴｅｋＰ－４ＨＢＰＡ、ＴｒｉｓＰ－ＨＡＰ、ＴｒｉｓＰ－ＰＡ、ＴｒｉｓＰ－ＳＡ、ＴｒｉｓＯＣＲ－ＰＡ、ＢｉｓＯＣＨＰ－Ｚ、ＢｉｓＰ－ＭＺ、ＢｉｓＰ－ＰＺ、ＢｉｓＰ－ＩＰＺ、ＢｉｓＯＣＰ－ＩＰＺ、ＢｉｓＰ－ＣＰ、ＢｉｓＲＳ－２Ｐ、ＢｉｓＲＳ－３Ｐ、ＢｉｓＰ－ＯＣＨＰ、メチレントリス－ＦＲ－ＣＲ、ＢｉｓＲＳ－２６Ｘ、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ジメチロール－ＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＢＰ、ＴＭＬ－ＨＱ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＡ、ＴＭＯＭ－ＢＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ（以上、商品名、本州化学工業製）、ＢＩＲ－ＯＣ、ＢＩＰ－ＰＣ、ＢＩＲ－ＰＣ、ＢＩＲ－ＰＴＢＰ、ＢＩＲ－ＰＣＨＰ、ＢＩＰ－ＢＩＯＣ－Ｆ、４ＰＣ、ＢＩＲ－ＢＩＰＣ－Ｆ、ＴＥＰ－ＢＩＰ－Ａ、４６ＤＭＯＣ、４６ＤＭＯＥＰ、ＴＭ－ＢＩＰ－Ａ（以上、商品名、旭有機材工業製）、２，６－ジメトキシメチル－４－ｔ－ブチルフェノール、２，６－ジメトキシメチル－ｐ－クレゾール、２，６－ジアセトキシメチル－ｐ－クレゾール、ナフトール、テトラヒドロキシベンゾフェノン、没食子酸メチルエステル、ビスフェノールＡ、ビスフェノールＥ、メチレンビスフェノール、ＢｉｓＰ－ＡＰ（商品名、本州化学工業製）、ノボラック樹脂などを挙げることができるが、これらに限定されない。 Specifically, as the hydroxy compound, phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (and above) , Product name, manufactured by Honshu Kagaku Kogyo), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMEEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6- Examples thereof include diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resin. , Not limited to these.
　アミノ化合物として具体的には、アニリン、メチルアニリン、ジエチルアミン、ブチルアミン、１，４－フェニレンジアミン、１，３－フェニレンジアミン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルフィドなどを挙げることができるが、これらに限定されない。 Specifically, the amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4. ′ -Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide and the like can be mentioned, but the present invention is not limited thereto.
　また、ポリヒドロキシポリアミノ化合物として具体的には、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、３，３’－ジヒドロキシベンジジンなどを挙げることができるが、これらに限定されない。 Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. ..
　これらの中でも、キノンジアジド化合物として、フェノール化合物および４－ナフトキノンジアジドスルホニル基とのエステルを含むことが好ましい。これによりｉ線露光に対するより高い感度と、より高い解像度を得ることができる。 Among these, it is preferable that the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
　本発明の樹脂組成物に用いるキノンジアジド化合物の含有量は、樹脂１００質量部に対して、１～５０質量部が好ましく、１０～４０質量部がより好ましい。キノンジアジド化合物の含有量をこの範囲とすることにより、露光部と未露光部のコントラストが得られることでより高感度化を図ることができるため好ましい。さらに増感剤などを必要に応じて添加してもよい。 The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin. It is preferable to set the content of the quinonediazide compound in this range because the contrast between the exposed portion and the unexposed portion can be obtained and the sensitivity can be further increased. Further, a sensitizer or the like may be added as needed.
　光酸発生剤は、オキシムスルホネート基を含む化合物（以下、単に「オキシムスルホネート化合物」ともいう）であることが好ましい。
　オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式（ＯＳ－１）、後述する式（ＯＳ－１０３）、式（ＯＳ－１０４）、又は、式（ＯＳ－１０５）で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（ＯＳ－１）中、Ｘ３は、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。Ｘ３が複数存在する場合は、それぞれ同一であってもよいし、異なっていてもよい。上記Ｘ３におけるアルキル基及びアルコキシ基は、置換基を有していてもよい。上記Ｘ３におけるアルキル基としては、炭素数１～４の、直鎖状又は分岐状アルキル基が好ましい。上記Ｘ３におけるアルコキシ基としては、炭素数１～４の直鎖状又は分岐状アルコキシ基が好ましい。上記Ｘ３におけるハロゲン原子としては、塩素原子又はフッ素原子が好ましい。
　式（ＯＳ－１）中、ｍ３は、０～３の整数を表し、０又は１が好ましい。ｍ３が２又は３であるとき、複数のＸ３は同一でも異なっていてもよい。
　式（ＯＳ－１）中、Ｒ３４は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～５のハロゲン化アルキル基、炭素数１～５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基であることが好ましい。Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～５のハロゲン化アルキル基又は炭素数１～５のハロゲン化アルコキシ基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基を表す。 In formula (OS- 1 ), X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s exist, they may be the same or different from each other. The alkyl group and the alkoxy group in X3 may have a substituent. As the alkyl group in X3 , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in X3 , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in X3 , a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3 , the plurality of X3s may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
　式（ＯＳ－１）中、ｍ３が３であり、Ｘ３がメチル基であり、Ｘ３の置換位置がオルト位であり、Ｒ３４が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、又は、ｐ－トリル基である化合物が特に好ましい。 In formula (OS-1), m3 is 3 , X3 is a methyl group , X3 is substituted at the ortho position, and R34 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
　式（ＯＳ－１）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号００６４～００６８、特開２０１５－１９４６７４号公報の段落番号０１５８～０１６７に記載された以下の化合物が例示され、これらの内容は本明細書に組み込まれる。 Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ１はアルキル基、アリール基又はヘテロアリール基を表し、複数存在する場合のあるＲｓ２はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、複数存在する場合のあるＲｓ６はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸｓはＯ又はＳを表し、ｎｓは１又は２を表し、ｍｓは０～６の整数を表す。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ１で表されるアルキル基（炭素数１～３０が好ましい）、アリール基（炭素数６～３０が好ましい）又はヘテロアリール基（炭素数４～３０が好ましい）は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2, which may be present in a plurality of R s2 , independently represents a hydrogen atom, an alkyl group and an aryl group. R s6 , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a known substituent as long as the effects of the present invention can be obtained.
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ２は、水素原子、アルキル基（炭素数１～１２が好ましい）又はアリール基（炭素数６～３０が好ましい）であることが好ましく、水素原子又はアルキル基であることがより好ましい。化合物中に２以上存在する場合のあるＲｓ２のうち、１つ又は２つがアルキル基、アリール基又はハロゲン原子であることが好ましく、１つがアルキル基、アリール基又はハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。Ｒｓ２で表されるアルキル基又はアリール基は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。
　式（ＯＳ－１０３）、式（ＯＳ－１０４）、又は、式（ＯＳ－１０５）中、ＸｓはＯ又はＳを表し、Ｏであることが好ましい。上記式（ＯＳ－１０３）～（ＯＳ－１０５）において、Ｘｓを環員として含む環は、５員環又は６員環である。 In the formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. Of the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、ｎｓは１又は２を表し、ＸｓがＯである場合、ｎｓは１であることが好ましく、また、ＸｓがＳである場合、ｎｓは２であることが好ましい。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ６で表されるアルキル基（炭素数１～３０が好ましい）及びアルキルオキシ基（炭素数１～３０が好ましい）は、置換基を有していてもよい。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、ｍｓは０～６の整数を表し、０～２の整数であることが好ましく、０又は１であることがより好ましく、０であることが特に好ましい。 In the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
　また、上記式（ＯＳ－１０３）で表される化合物は、下記式（ＯＳ－１０６）、式（ＯＳ－１１０）又は式（ＯＳ－１１１）で表される化合物であることが特に好ましく、上記式（ＯＳ－１０４）で表される化合物は、下記式（ＯＳ－１０７）で表される化合物であることが特に好ましく、上記式（ＯＳ－１０５）で表される化合物は、下記式（ＯＳ－１０８）又は式（ＯＳ－１０９）で表される化合物であることが特に好ましい。
Figure JPOXMLDOC01-appb-C000030
 Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
Figure JPOXMLDOC01-appb-C000030
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ１はアルキル基、アリール基又はヘテロアリール基を表し、Ｒｔ７は、水素原子又は臭素原子を表し、Ｒｔ８は水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒｔ９は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒｔ２は水素原子又はメチル基を表す。
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ７は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R t2 represents a hydrogen atom or a methyl group.
In the formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ８は、水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、炭素数１～８のアルキル基、ハロゲン原子又はフェニル基であることが好ましく、炭素数１～８のアルキル基であることがより好ましく、炭素数１～６のアルキル基であることが更に好ましく、メチル基であることが特に好ましい。 In formulas (OS-106) to (OS-111), R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ９は、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、水素原子であることが好ましい。
　Ｒｔ２は、水素原子又はメチル基を表し、水素原子であることが好ましい。
　また、上記オキシムスルホネート化合物において、オキシムの立体構造（Ｅ，Ｚ）については、いずれか一方であっても、混合物であってもよい。
　上記式（ＯＳ－１０３）～式（ＯＳ－１０５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号００８８～００９５、特開２０１５－１９４６７４号公報の段落番号０１６８～０１９４に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In the formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
　オキシムスルホネート基を少なくとも１つを含むオキシムスルホネート化合物の好適な他の態様としては、下記式（ＯＳ－１０１）、式（ＯＳ－１０２）で表される化合物が挙げられる。 Other suitable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ９は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基又はヘテロアリール基を表す。Ｒｕ９がシアノ基又はアリール基である態様がより好ましく、Ｒｕ９がシアノ基、フェニル基又はナフチル基である態様が更に好ましい。
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ２ａは、アルキル基又はアリール基を表す。
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｘｕは、－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲｕ５－、－ＣＨ２－、－ＣＲｕ６Ｈ－又はＣＲｕ６Ｒｕ７－を表し、Ｒｕ５～Ｒｕ７はそれぞれ独立に、アルキル基又はアリール基を表す。 In the formula (OS-101) or the formula (OS-102), Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group. The embodiment in which R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5- , -CH 2- , -CR u6 H- or CR u6 R u7. -, R u5 to R u7 independently represent an alkyl group or an aryl group, respectively.
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ１～Ｒｕ４はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基又はアリール基を表す。Ｒｕ１～Ｒｕ４のうちの２つがそれぞれ互いに結合して環を形成してもよい。このとき、環が縮環してベンゼン環ともに縮合環を形成していてもよい。Ｒｕ１～Ｒｕ４としては、水素原子、ハロゲン原子又はアルキル基が好ましく、また、Ｒｕ１～Ｒｕ４のうちの少なくとも２つが互いに結合してアリール基を形成する態様も好ましい。中でも、Ｒｕ１～Ｒｕ４がいずれも水素原子である態様が好ましい。上記した置換基は、いずれも、更に置換基を有していてもよい。 In the formula (OS-101) or the formula (OS-102), Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. Two of R u1 to R u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a fused ring together with the benzene ring. As R u1 to Ru4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of Ru1 to Ru4 are bonded to each other to form an aryl group is also preferable. Above all, it is preferable that all of Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
　上記式（ＯＳ－１０１）で表される化合物は、式（ＯＳ－１０２）で表される化合物であることがより好ましい。
　また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
　式（ＯＳ－１０１）で表される化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号０１０２～０１０６、特開２０１５－１９４６７４号公報の段落番号０１９５～０２０７に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
　上記化合物の中でも、下記ｂ－９、ｂ－１６、ｂ－３１、ｂ－３３が好ましい。
Figure JPOXMLDOC01-appb-C000032
 　市販品としては、ＷＰＡＧ－３３６（富士フイルム和光純薬（株）製）、ＷＰＡＧ－４４３（富士フイルム和光純薬（株）製）、ＭＢＺ－１０１（みどり化学（株）製）等を挙げることができる。 The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.
Figure JPOXMLDOC01-appb-C000032
 Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like. Can be done.
　また、下記構造式で表される化合物も好ましい例として挙げられる。
Figure JPOXMLDOC01-appb-C000033
 Further, a compound represented by the following structural formula is also mentioned as a preferable example.
Figure JPOXMLDOC01-appb-C000033
　有機ハロゲン化化合物としては、具体的には、若林等「Ｂｕｌｌ　Ｃｈｅｍ．Ｓｏｃ　Ｊａｐａｎ」４２、２９２４（１９６９）、米国特許第３，９０５，８１５号明細書、特公昭４６－４６０５号、特開昭４８－３６２８１号公報、特開昭５５－３２０７０号公報、特開昭６０－２３９７３６号公報、特開昭６１－１６９８３５号公報、特開昭６１－１６９８３７号公報、特開昭６２－５８２４１号公報、特開昭６２－２１２４０１号公報、特開昭６３－７０２４３号公報、特開昭６３－２９８３３９号公報、Ｍ．Ｐ．Ｈｕｔｔ“Ｊｕｒｎａｌ　ｏｆ　Ｈｅｔｅｒｏｃｙｃｌｉｃ　Ｃｈｅｍｉｓｔｒｙ”１（Ｎｏ３），（１９７０）などに記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。特に、トリハロメチル基が置換したオキサゾール化合物：Ｓ－トリアジン化合物が好ましい例として挙げられる。
　より好適には、すくなくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がｓ－トリアジン環に結合したｓ－トリアジン誘導体、具体的には、例えば、２，４，６－トリス（モノクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジクロロメチル）－ｓ－トリアジン、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２―ｎ－プロピル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（α，α，β－トリクロロエチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（３，４－エポキシフェニル）－４、６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－クロロフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔１－（ｐ－メトキシフェニル）－２，４－ブタジエニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－スチリル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－ｉ－プロピルオキシスチリル）－４、６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ナトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ベンジルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジブロモメチル）－ｓ－トリアジン、２，４，６－トリス（トリブロモメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリブロモメチル）－ｓ－トリアジン、２－メトキシ－４，６－ビス（トリブロモメチル）－ｓ－トリアジン等が挙げられる。 Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like are mentioned, and the contents thereof are incorporated in the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound is given as a preferable example.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
　有機ホウ酸塩化合物としては、例えば、特開昭６２－１４３０４４号公報、特開昭６２－１５０２４２号公報、特開平９－１８８６８５号公報、特開平９－１８８６８６号公報、特開平９－１８８７１０号公報、特開２０００－１３１８３７号公報、特開２００２－１０７９１６号公報、特許第２７６４７６９号公報、特開２００２－１１６５３９号公報、等、及び、Ｋｕｎｚ，Ｍａｒｔｉｎ“Ｒａｄ　Ｔｅｃｈ'９８．Ｐｒｏｃｅｅｄｉｎｇ　Ａｐｒｉｌ　１９－２２，１９９８，Ｃｈｉｃａｇｏ”等に記載される有機ホウ酸塩、特開平６－１５７６２３号公報、特開平６－１７５５６４号公報、特開平６－１７５５６１号公報に記載の有機ホウ素スルホニウム錯体或いは有機ホウ素オキソスルホニウム錯体、特開平６－１７５５５４号公報、特開平６－１７５５５３号公報に記載の有機ホウ素ヨードニウム錯体、特開平９－１８８７１０号公報に記載の有機ホウ素ホスホニウム錯体、特開平６－３４８０１１号公報、特開平７－１２８７８５号公報、特開平７－１４０５８９号公報、特開平７－３０６５２７号公報、特開平７－２９２０１４号公報等の有機ホウ素遷移金属配位錯体等が具体例として挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent Application Laid-Open No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98. , 1998, Chicago ”, etc., the organic boron sulfonium complex or the organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561. Complex, organic boron iodonium complex described in JP-A-6-175554, JP-A-6-175553, organic boron phosphonium complex described in JP-A-9-188710, JP-A-6-348011, JP-A. Specific examples thereof include organic boron transition metal coordination complexes such as JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Incorporated herein.
　ジスルホン化合物としては、特開昭６１－１６６５４４号公報、特願２００１－１３２３１８公報等に記載されている化合物およびジアゾジスルホン化合物が挙げられる。 Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
　上記オニウム塩化合物としては、例えば、Ｓ．Ｉ．Ｓｃｈｌｅｓｉｎｇｅｒ，Ｐｈｏｔｏｇｒ．Ｓｃｉ．Ｅｎｇ．，１８，３８７（１９７４）、Ｔ．Ｓ．Ｂａｌ　ｅｔ　ａｌ，Ｐｏｌｙｍｅｒ，２１，４２３（１９８０）に記載のジアゾニウム塩、米国特許第４，０６９，０５５号明細書、特開平４－３６５０４９号公報等に記載のアンモニウム塩、米国特許第４，０６９，０５５号、同４，０６９，０５６号の各明細書に記載のホスホニウム塩、欧州特許第１０４、１４３号、米国特許第３３９，０４９号、同第４１０，２０１号の各明細書、特開平２－１５０８４８号、特開平２－２９６５１４号公報に記載のヨードニウム塩、欧州特許第３７０，６９３号、同３９０，２１４号、同２３３，５６７号、同２９７，４４３号、同２９７，４４２号、米国特許第４，９３３，３７７号、同１６１，８１１号、同４１０，２０１号、同３３９，０４９号、同４，７６０，０１３号、同４，７３４，４４４号、同２，８３３，８２７号、独国特許第２，９０４，６２６号、同３，６０４，５８０号、同３，６０４，５８１号の各明細書に記載のスルホニウム塩、Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏ　ｅｔ　ａｌ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１０（６），１３０７（１９７７）、Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏ　ｅｔ　ａｌ，Ｊ．Ｐｏｌｙｍｅｒ　Ｓｃｉ．，Ｐｏｌｙｍｅｒ　Ｃｈｅｍ．Ｅｄ．，１７，１０４７（１９７９）に記載のセレノニウム塩、Ｃ．Ｓ．Ｗｅｎ　ｅｔ　ａｌ，Ｔｅｈ，Ｐｒｏｃ．Ｃｏｎｆ．Ｒａｄ．Ｃｕｒｉｎｇ　ＡＳＩＡ，ｐ４７８　Ｔｏｋｙｏ，Ｏｃｔ（１９８８）に記載のアルソニウム塩、ピリジニウム塩等のオニウム塩等が挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, European Patents 104, 143, US Patents 339, 049, 410, 201, Japanese Patent Application Laid-Open No. Iodonium salt described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 370,693, 390,214, 233,567, 297,443, 297,442, US Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 The sulfonium salt according to each specification of German Patent No. 2,904,626, 3,604,580, and 3,604,581. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as alsonium salt and pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988), and these contents are incorporated in the present specification.
　オニウム塩としては、下記一般式（ＲＩ－Ｉ）～（ＲＩ－ＩＩＩ）で表されるオニウム塩が挙げられる。
Figure JPOXMLDOC01-appb-C000034
 　式（ＲＩ－Ｉ）中、Ａｒ１１は置換基を１～６有していても良い炭素数２０以下のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数６～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のアルキルアミノ基、炭素数２～１２のジアルキルアミノ基、アルキル基の炭素数が１～１２のアルキルアミド基又はアリール基の炭素数が６～２０のアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ１１ －は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式（ＲＩ－ＩＩ）中、Ａｒ２１、Ａｒ２２は各々独立に置換基を１～６有していてもよい炭素数１～２０のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ２１－は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式（ＲＩ－ＩＩＩ）中、Ｒ３１、Ｒ３２、Ｒ３３は各々独立に置換基を１～６有していても良い炭素数６～２０のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に炭素数１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ３１ －は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
Figure JPOXMLDOC01-appb-C000034
 In the formula (RI-I), Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms. ~ 12 alkenyl groups, alkynyl groups with 2-12 carbon atoms, aryl groups with 6-12 carbon atoms, alkoxy groups with 1-12 carbon atoms, allyloxy groups with 1-12 carbon atoms, halogen atoms, 1-12 carbon atoms Alkylamino group, dialkylamino group with 2 to 12 carbon atoms, alkylamide group with 1 to 12 carbon atoms or arylamide group with 6 to 20 carbon atoms, carbonyl group, carboxy group, cyano Examples thereof include a group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable. From the aspect, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable. In the formula (RI-II), Ar 21 and Ar 22 each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group with 2 to 12 carbon atoms, alkynyl group with 2 to 12 carbon atoms, aryl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, allyloxy group with 1 to 12 carbon atoms, halogen An atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of the alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in the alkyl group, Examples thereof include a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R 31 , R 32 , and R 33 each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. An aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of each other, and an alkyl group having 1 to 12 carbon atoms. Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability. From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
　好ましい光酸発生剤の具体例としては、以下のものが挙げられる。
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
 Specific examples of preferable photoacid generators include the following.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
　光酸発生剤は、樹脂組成物の全固形分に対し、０．１～２０質量％使用することが好ましく、０．５～１８質量％使用することがより好ましく、０．５～１０質量％使用することが更に好ましく、０．５～３質量％使用することが一層好ましく、０．５～１．２質量％使用することがより一層好ましい。
　光酸発生剤は、１種単独で使用されても、複数種の組み合わせで使用されてもよい。複数種の組み合わせの場合には、それらの合計量が上記範囲にあることが好ましい。
　また、所望の光源に対して、感光性を付与する為、増感剤と併用することも好ましい。 The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
The photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.
It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.
＜溶剤＞
　本発明の樹脂組成物は、溶剤を含む。
　溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition of the present invention contains a solvent.
As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸へキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル、ヘキサン酸エチル、ヘプタン酸エチル、マロン酸ジメチル、マロン酸ジエチル等が好適なものとして挙げられる。 Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples thereof include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..
　エーテル類として、例えば、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノプロピルエーテルアセテート、ジプロピレングリコールジメチルエーテル等が好適なものとして挙げられる。 Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like.
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、３－メチルシクロヘキサノン、レボグルコセノン、ジヒドロレボグルコセノン等が好適なものとして挙げられる。 As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
　環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類が好適なものとして挙げられる。 As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
　スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。 As the sulfoxides, for example, dimethyl sulfoxide is preferable.
　アミド類として、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－シクロヘキシル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルイソブチルアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、Ｎ－ホルミルモルホリン、Ｎ－アセチルモルホリン等が好適なものとして挙げられる。 As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, Suitable examples include 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.
　ウレア類として、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア、１，３－ジメチル－２－イミダゾリジノン等が好適なものとして挙げられる。 As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
　アルコール類として、メタノール、エタノール、１-プロパノール、２-プロパノール、１－ブタノール、１－ペンタノール、１－ヘキサノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、１－メトキシ－２－プロパノール、２－エトキシエタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコール、テトラエチレングリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、メチルフェニルカルビノール、ｎ－アミルアルコール、メチルアミルアルコール、および、ダイアセトンアルコール等が挙げられる。 Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
　溶剤は、塗布面性状の改良などの観点から、２種以上を混合する形態も好ましい。 The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
　本発明では、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、Ｎ－メチル－２－ピロリドン、プロピレングリコールメチルエーテル、及びプロピレングリコールメチルエーテルアセテート、レボグルコセノン、ジヒドロレボグルコセノンから選択される１種の溶剤、又は、２種以上で構成される混合溶剤が好ましい。ジメチルスルホキシドとγ－ブチロラクトンとの併用、又は、Ｎ－メチル－２－ピロリドンと乳酸エチルとの併用が特に好ましい。 In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- One solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone, Alternatively, a mixed solvent composed of two or more kinds is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferable.
　溶剤の含有量は、塗布性の観点から、本発明の樹脂組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７５質量％となる量にすることがより好ましく、１０～７０質量％となる量にすることが更に好ましく、２０～７０質量％となるようにすることが一層好ましい。溶剤含有量は、塗膜の所望の厚さと塗布方法に応じて調節すればよい。 From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
　本発明の樹脂組成物は、溶剤を１種のみ含有していてもよいし、２種以上含有していてもよい。溶剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
＜酸捕捉剤＞
　本発明の樹脂組成物は、露光から加熱までの経時による性能変化を低減するために、酸捕捉剤を含有することが好ましい。ここで酸捕捉剤とは、系中に存在することで発生酸を捕捉することができる化合物を指し、酸性度が低くｐＫａの高い化合物であることが好ましい。酸捕捉剤としては、アミノ基を有する化合物が好ましく、１級アミン、２級アミン、３級アミン、アンモニウム塩、３級アミドなどが好ましく、１級アミン、２級アミン、３級アミン、アンモニウム塩が好ましく、２級アミン、３級アミン、アンモニウム塩がより好ましい。
　酸捕捉剤としては、イミダゾール構造、ジアザビシクロ構造、オニウム構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び／又はエーテル結合を有するアルキルアミン誘導体、水酸基及び／又はエーテル結合を有するアニリン誘導体等を好ましく挙げることができる。オニウム構造を有する場合、酸捕捉剤はアンモニウム、ジアゾニウム、ヨードニウム、スルホニウム、ホスホニウム、ピリジニウムなどから選択されるカチオンと、酸発生剤が発生する酸より酸性度の低い酸のアニオンとを有する塩であることが好ましい。 <Acid scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance with time from exposure to heating. Here, the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable. Is preferable, and secondary amines, tertiary amines, and ammonium salts are more preferable.
Examples of the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
　イミダゾール構造を有する酸捕捉剤としてはイミダゾール、２、４、５－トリフェニルイミダゾール、ベンズイミダゾール、２－フェニルベンゾイミダゾール等が挙げられる。ジアザビシクロ構造を有する酸捕捉剤としては１、４－ジアザビシクロ［２，２，２］オクタン、１、５－ジアザビシクロ［４，３，０］ノナ－５－エン、１、８－ジアザビシクロ［５，４，０］ウンデカー７－エン等が挙げられる。オニウム構造を有する酸捕捉剤としてはテトラブチルアンモニウムヒドロキシド、トリアリールスルホニウムヒドロキシド、フェナシルスルホニウムヒドロキシド、２－オキソアルキル基を有するスルホニウムヒドロキシド、具体的にはトリフェニルスルホニウムヒドロキシド、トリス（ｔ－ブチルフェニル）スルホニウムヒドロキシド、ビス（ｔ－ブチルフェニル）ヨードニウムヒドロキシド、フェナシルチオフェニウムヒドロキシド、２－オキソプロピルチオフェニウムヒドロキシド等が挙げられる。トリアルキルアミン構造を有する酸捕捉剤としては、トリ（ｎ－ブチル）アミン、トリ（ｎ－オクチル）アミン等を挙げることができる。アニリン構造を有する酸捕捉剤としては、２，６－ジイソプロピルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジブチルアニリン、Ｎ，Ｎ－ジヘキシルアニリン等を挙げることができる。ピリジン構造を有する酸捕捉剤としては、ピリジン、４－メチルピリジン等を挙げることができる。水酸基及び／又はエーテル結合を有するアルキルアミン誘導体としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－フェニルジエタノールアミン、トリス（メトキシエトキシエチル）アミン等を挙げることができる。水酸基及び／又はエーテル結合を有するアニリン誘導体としては、Ｎ，Ｎ－ビス（ヒドロキシエチル）アニリン等を挙げることができる。 Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like. As an acid scavenger having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like. Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
　好ましい酸捕捉剤の具体例としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン、ジエチルアミン、トリエチルアミン、ヘキシルアミン、ドデシルアミン、シクロヘキシルアミン、シクロヘキシルメチルアミン、シクロヘキシルジメチルアミン、アニリン、Ｎ－メチルアニリン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミン、ピリジン、ブチルアミン、イソブチルアミン、ジブチルアミン、トリブチルアミン、ジシクロヘキシルアミン、ＤＢＵ（ジアザビシクロウンデセン）、ＤＡＢＣＯ（１，４－ジアザビシクロ［２．２．２］オクタン）、Ｎ，Ｎ－ジイソプロピルエチルアミン、テトラメチルアンモニウムヒドロキシド、エチレンジアミン、１，５－ジアミノペンタン、Ｎ－メチルヘキシルアミン、Ｎ－メチルジシクロヘキシルアミン、トリオクチルアミン、Ｎ－エチルエチレンジアミン、Ｎ，Ｎ―ジエチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラブチルー１，６－ヘキサンジアミン、スペルミジン、ジアミノシクロヘキサン、ビス（２－メトキシエチル）アミン、ピペリジン、メチルピペリジン、ピペラジン、トロパン、Ｎ－フェニルベンジルアミン、１，２－ジアニリノエタン、２－アミノエタノール、トルイジン、アミノフェノール、ヘキシルアニリン、フェニレンジアミン、フェニルエチルアミン、ジベンジルアミン、ピロール、Ｎ－メチルピロール、グアニジン、アミノピロリジン、ピラゾール、ピラゾリン、アミノモルホリン、アミノアルキルモルフォリン等があげられる。 Specific examples of preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N. , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N, N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin, piperazine, tropane, N-phenylbenzylamine, 1, 2 -Dianilinoetan, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrol, N-methylpyrol, guanidine, aminopyrrolidin, pyrazole, pyrazoline, aminomorpholin, aminoalkylmorpholin, etc. Can be given.
　これらの酸捕捉剤は、１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
本発明に係る組成物は、酸捕捉剤を含有してもしなくてもよいが、含有する場合、酸捕捉剤の含有量は、組成物の全固形分を基準として、通常は０．００１～１０質量％であり、好ましくは０．０１～５質量％である。 These acid scavengers may be used alone or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
　酸発生剤と酸捕捉剤との使用割合は、酸発生剤／酸捕捉剤（モル比）＝２．５～３００であることが好ましい。即ち、感度、解像度の点からモル比が２．５以上であることが好ましく、露光後加熱処理までの経時でのレリーフパターンの太りによる解像度の低下抑制の点から３００以下が好ましい。酸発生剤／酸捕捉剤（モル比）は、より好ましくは５．０～２００、更に好ましくは７．０～１５０である。 The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time from the exposure to the heat treatment. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
＜熱硬化促進剤＞
　樹脂組成物は、熱硬化促進剤を含んでもよい。
　熱硬化促進剤としては、熱重合開始剤、熱酸発生剤等が挙げられる。
　樹脂組成物が重合性化合物としてラジカル架橋剤を含む場合は熱重合開始剤を、他の架橋剤を含む場合は熱酸発生剤を含む態様が挙げられる。 <Thermosetting accelerator>
The resin composition may contain a thermosetting accelerator.
Examples of the thermosetting accelerator include a thermal polymerization initiator, a thermal acid generator and the like.
When the resin composition contains a radical cross-linking agent as the polymerizable compound, a thermal polymerization initiator is included, and when the resin composition contains another cross-linking agent, a thermal acid generator is included.
〔熱重合開始剤〕
　熱重合開始剤としては、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。
　熱ラジカル重合開始剤として、具体的には、特開２００８－０６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられ、この内容は本明細書に組み込まれる。 [Thermal polymerization initiator]
As the thermal polymerization initiator, a thermal radical polymerization initiator may be particularly contained. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound.
Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
　熱重合開始剤を含む場合、その含有量は、本発明の樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、更に好ましくは０．５～１５質量％である。熱重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。熱重合開始剤を２種以上含有する場合は、合計量が上記範囲であることが好ましい。 When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
〔熱酸発生剤〕
　樹脂組成物は、熱酸発生剤を含んでもよい。
　熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも１種の化合物の架橋反応を促進させる効果がある。 [Thermal acid generator]
The resin composition may contain a thermal acid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
　熱酸発生剤の熱分解開始温度は、５０℃～２７０℃が好ましく、５０℃～２５０℃がより好ましい。また、組成物を基板に塗布した後の乾燥（プリベーク：約７０～１４０℃）時には酸を発生せず、その後の露光、現像でパターニングした後の最終加熱（キュア：約１００～４００℃）時に酸を発生するものを熱酸発生剤として選択すると、現像時の感度低下を抑制できるため好ましい。
　熱分解開始温度は、熱酸発生剤を耐圧カプセル中５℃／分で５００℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
　熱分解開始温度を測定する際に用いられる機器としては、Ｑ２０００（ＴＡインスツルメント社製）等が挙げられる。 The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
　熱酸発生剤から発生する酸は強酸が好ましく、例えば、ｐ－トルエンスルホン酸、ベンゼンスルホン酸などのアリールスルホン酸、メタンスルホン酸、エタンスルホン酸、ブタンスルホン酸などのアルキルスルホン酸、あるいはトリフルオロメタンスルホン酸などのハロアルキルスルホン酸などが好ましい。このような熱酸発生剤の例としては、特開２０１３－０７２９３５号公報の段落００５５に記載のものが挙げられる。 The acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935.
　中でも、硬化物（硬化膜）中の残留が少なく硬化物（硬化膜）物性を低下させにくいという観点から、炭素数１～４のアルキルスルホン酸や炭素数１～４のハロアルキルスルホン酸を発生するものがより好ましく、メタンスルホン酸（４－ヒドロキシフェニル）ジメチルスルホニウム、メタンスルホン酸（４－（（メトキシカルボニル）オキシ）フェニル）ジメチルスルホニウム、メタンスルホン酸ベンジル（４－ヒドロキシフェニル）メチルスルホニウム、メタンスルホン酸ベンジル（４－（（メトキシカルボニル）オキシ）フェニル）メチルスルホニウム、メタンスルホン酸（４－ヒドロキシフェニル）メチル（（２－メチルフェニル）メチル）スルホニウム、トリフルオロメタンスルホン酸（４－ヒドロキシフェニル）ジメチルスルホニウム、トリフルオロメタンスルホン酸（４－（（メトキシカルボニル）オキシ）フェニル）ジメチルスルホニウム、トリフルオロメタンスルホン酸ベンジル（４－ヒドロキシフェニル）メチルスルホニウム、トリフルオロメタンスルホン酸ベンジル（４－（（メトキシカルボニル）オキシ）フェニル）メチルスルホニウム、トリフルオロメタンスルホン酸（４－ヒドロキシフェニル）メチル（（２－メチルフェニル）メチル）スルホニウム、３－（５－（（（プロピルスルホニル）オキシ）イミノ）チオフェン－２（５Ｈ）－イリデン）－２－（ｏ－トリル）プロパンニトリル、２，２－ビス（３－（メタンスルホニルアミノ）－４－ヒドロキシフェニル）ヘキサフルオロプロパンが、熱酸発生剤として好ましい。 Above all, from the viewpoint that there is little residue in the cured product (cured film) and it is difficult to deteriorate the physical properties of the cured product (cured film), alkyl sulfonic acid having 1 to 4 carbon atoms and haloalkyl sulfonic acid having 1 to 4 carbon atoms are generated. More preferably, methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, methanesulfonic acid. Benzyl acid (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium , Trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) ) Methyl sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-Trill) propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as the thermal acid generator.
　また、特開２０１３－１６７７４２号公報の段落００５９に記載の化合物も熱酸発生剤として好ましい。 Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermal acid generator.
　熱酸発生剤の含有量は、樹脂１００質量部に対して０．０１質量部以上が好ましく、０．１質量部以上がより好ましい。０．０１質量部以上含有することで、架橋反応が促進されるため、硬化物（硬化膜）の機械特性及び耐溶剤性をより向上させることができる。また、硬化物（硬化膜）の電気絶縁性の観点から、２０質量部以下が好ましく、１５質量部以下がより好ましく、１０質量部以下が更に好ましい。 The content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin. By containing 0.01 part by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the cured product (cured film) can be further improved. Further, from the viewpoint of electrical insulation of the cured product (cured film), 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
＜塩基発生剤＞
　本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明の樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
　特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
　塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、２級アミン、３級アミンが挙げられる。
　本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α－アミノアセトフェノン誘導体化合物、４級アンモニウム塩誘導体化合物、ピリジニウム塩、α－ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式（Ｂ１）、式（Ｂ２）、又は式（Ｂ３）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000039
 <Base generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and a known base generator can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides. Compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
Figure JPOXMLDOC01-appb-C000039
　式（Ｂ１）及び式（Ｂ２）中、Ｒｂ１、Ｒｂ２及びＲｂ３はそれぞれ独立に、第三級アミン構造を有しない有機基、ハロゲン原子又は水素原子である。ただし、Ｒｂ１及びＲｂ２が同時に水素原子となることはない。また、Ｒｂ１、Ｒｂ２及びＲｂ３はいずれもカルボキシ基を有することはない。なお、本明細書で第三級アミン構造とは、３価の窒素原子の３つの結合手がいずれも炭化水素系の炭素原子と共有結合している構造を指す。したがって、結合した炭素原子がカルボニル基をなす炭素原子の場合、つまり窒素原子とともにアミド基を形成する場合はこの限りではない。 In the formula (B1) and the formula (B2), Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
　式（Ｂ１）、（Ｂ２）中、Ｒｂ１、Ｒｂ２及びＲｂ３は、これらのうち少なくとも１つが環状構造を含むことが好ましく、少なくとも２つが環状構造を含むことがより好ましい。環状構造としては、単環及び縮合環のいずれであってもよく、単環又は単環が２つ縮合した縮合環が好ましい。単環は、５員環又は６員環が好ましく、６員環が好ましい。単環は、シクロヘキサン環及びベンゼン環が好ましく、シクロヘキサン環がより好ましい。 In the formulas (B1) and (B2), it is preferable that at least one of Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
　より具体的にＲｂ１及びＲｂ２は、水素原子、アルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、又はアリールアルキル基（炭素数７～２５が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であることが好ましい。これらの基は、本発明の効果を奏する範囲で置換基を有していてもよい。Ｒｂ１とＲｂ２とは互いに結合して環を形成していてもよい。形成される環としては、４～７員の含窒素複素環が好ましい。Ｒｂ１及びＲｂ２は特に、置換基を有してもよい直鎖、分岐、又は環状のアルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）であることが好ましく、置換基を有してもよいシクロアルキル基（炭素数３～２４が好ましく、３～１８がより好ましく、３～１２が更に好ましい）であることがより好ましく、置換基を有してもよいシクロヘキシル基が更に好ましい。 More specifically, Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. Maybe cyclohexyl groups are more preferred.
　Ｒｂ３としては、アルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１２がより好ましく、２～６が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）、アリールアルケニル基（炭素数８～２４が好ましく、８～２０がより好ましく、８～１６が更に好ましい）、アルコキシル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリールオキシ基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、又はアリールアルキルオキシ基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）が挙げられる。中でも、シクロアルキル基（炭素数３～２４が好ましく、３～１８がより好ましく、３～１２が更に好ましい）、アリールアルケニル基、アリールアルキルオキシ基が好ましい。Ｒｂ３は更に本発明の効果を奏する範囲で置換基を有していてもよい。 Examples of Rb 3 include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18). ~ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24). 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). Among them, a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
　式（Ｂ１）で表される化合物は、下記式（Ｂ１－１）又は下記式（Ｂ１－２）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000040
 The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
Figure JPOXMLDOC01-appb-C000040
　式中、Ｒｂ１１及びＲｂ１２、並びに、Ｒｂ３１及びＲｂ３２は、それぞれ、式（Ｂ１）におけるＲｂ１及びＲｂ２と同じである。
　Ｒｂ１３はアルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Ｒｂ１３はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb 13 is preferably an arylalkyl group.
　Ｒｂ３３及びＲｂ３４は、それぞれ独立に、水素原子、アルキル基（炭素数１～１２が好ましく、１～８がより好ましく、１～３が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～８がより好ましく、２～３が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が更に好ましい）であり、水素原子が好ましい。 Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), and arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
　Ｒｂ３５は、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、３～８が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～１０がより好ましく、３～８が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、アリール基が好ましい。 Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms are preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
　式（Ｂ１－１）で表される化合物は、式（Ｂ１－１ａ）で表される化合物もまた好ましい。
Figure JPOXMLDOC01-appb-C000041
 As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.
Figure JPOXMLDOC01-appb-C000041
　Ｒｂ１１及びＲｂ１２は式（Ｂ１－１）におけるＲｂ１１及びＲｂ１２と同義である。
　Ｒｂ１５及びＲｂ１６は水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が更に好ましい）であり、水素原子又はメチル基が好ましい。
　Ｒｂ１７はアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、３～８が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～１０がより好ましく、３～８が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
Figure JPOXMLDOC01-appb-C000042
 （Ｂ３）
Figure JPOXMLDOC01-appb-C000042
 (B3)
　式（Ｂ３）において、Ｌは、隣接する酸素原子と炭素原子を連結する連結鎖の経路上に飽和炭化水素基を有する２価の炭化水素基であって、連結鎖の経路上の原子数が３以上である炭化水素基を表す。また、ＲＮ１およびＲＮ２は、それぞれ独立に１価の有機基を表す。 In the formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more. Further, RN1 and RN2 each independently represent a monovalent organic group.
　本明細書において、「連結鎖」とは、連結対象の２つの原子または原子群の間を結ぶ経路上の原子鎖のうち、これらの連結対象を最短（最小原子数）で結ぶものをいう。例えば、下記式で表される化合物において、Ｌは、フェニレンエチレン基から構成され、飽和炭化水素基としてエチレン基を有し、連結鎖は４つの炭素原子から構成されており、連結鎖の経路上の原子数（つまり、連結鎖を構成する原子の数であり、以下、「連結鎖長」あるいは「連結鎖の長さ」ともいう。）は４である。
Figure JPOXMLDOC01-appb-C000043
 As used herein, the term "linking chain" refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length") is 4.
Figure JPOXMLDOC01-appb-C000043
　式（Ｂ３）におけるＬ中の炭素数（連結鎖中の炭素原子以外の炭素原子も含む）は、３～２４であることが好ましい。上限は、１２以下であることがより好ましく、１０以下であることがさらに好ましく、８以下であることが特に好ましい。下限は、４以上であることがより好ましい。上記分子内環化反応を速やかに進行させる観点から、Ｌの連結鎖長の上限は、１２以下であることが好ましく、８以下であることがより好ましく、６以下であることがさらに好ましく、５以下であることが特に好ましい。特に、Ｌの連結鎖長は、４または５であることが好ましく、４であることが最も好ましい。塩基発生剤の具体的な好ましい化合物としては、例えば、国際公開第２０２０／０６６４１６号の段落番号０１０２～０１６８に記載の化合物、国際公開第２０１８／０３８００２号の段落番号０１４３～０１７７に記載の化合物も挙げられる。 The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linked chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable. In particular, the chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
また、塩基発生剤は下記式（Ｎ１）で表される化合物を含むことも好ましい。
Figure JPOXMLDOC01-appb-C000044
 Further, it is also preferable that the base generator contains a compound represented by the following formula (N1).
Figure JPOXMLDOC01-appb-C000044
　式（Ｎ１）中、ＲＮ１およびＲＮ２はそれぞれ独立に１価の有機基を表し、ＲC1は水素原子または保護基を表し、Ｌは２価の連結基を表す。 In formula ( N1 ), RN1 and RN2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.
　Ｌは２価の連結基であり、２価の有機基であることが好ましい。連結基の連結鎖長は１以上であることが好ましく、２以上であることがより好ましい。上限としては、１２以下であることが好ましく、８以下であることがより好ましく、５以下であることがさらに好ましい。連結鎖長とは、式中の２つのカルボニル基の間において最短の道程となる原子配列に存在する原子の数である。 L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.
　式（Ｎ１）中、ＲＮ１およびＲＮ２はそれぞれ独立に１価の有機基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２がさらに好ましい）を表し、炭化水素基（炭素数１～２４が好ましく、１～１２がより好ましく、１～１０がさらに好ましい）であることが好ましく、具体的には、脂肪族炭化水素基（炭素数１～２４が好ましく、１～１２がより好ましく、１～１０がさらに好ましい）または芳香族炭化水素基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）を挙げることができ、脂肪族炭化水素基が好ましい。ＲＮ１およびＲＮ２として、脂肪族炭化水素基を用いると、発生する塩基の塩基性が高く好ましい。なお、脂肪族炭化水素基および芳香族炭化水素基は、置換基を有していてもよく、また、脂肪族炭化水素基および芳香族炭化水素基が脂肪族炭化水素鎖中や芳香環中、置換基中に酸素原子を有していてもよい。特に、脂肪族炭化水素基が炭化水素鎖中に酸素原子を有している態様が例示される。 In the formula ( N1 ), RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred. It is preferable to use an aliphatic hydrocarbon group as RN1 and RN2 because the basicity of the generated base is high. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
　ＲＮ１およびＲＮ２を構成する脂肪族炭化水素基としては、直鎖または分岐の鎖状アルキル基、環状アルキル基、鎖状アルキル基と環状アルキル基の組合せに係る基、酸素原子を鎖中に有するアルキル基が挙げられる。直鎖または分岐の鎖状アルキル基は、炭素数１～２４のものが好ましく、２～１８がより好ましく、３～１２がさらに好ましい。直鎖または分岐の鎖状アルキル基は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソプロピル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、イソペンチル基、ネオペンチル基、ターシャリーペンチル基、イソヘキシル基等が挙げられる。
　環状アルキル基は、炭素数３～１２のものが好ましく、３～６がより好ましい。環状アルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等が挙げられる。
　鎖状アルキル基と環状アルキル基の組合せに係る基は、炭素数４～２４のものが好ましく、４～１８がより好ましく、４～１２がさらに好ましい。鎖状アルキル基と環状アルキル基の組合せに係る基は、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基、シクロヘキシルプロピル基、メチルシクロヘキシルメチル基、エチルシクロヘキシルエチル基等が挙げられる。
　酸素原子を鎖中に有するアルキル基は、炭素数２～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。酸素原子を鎖中に有するアルキル基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。
　なかでも、後述する分解生成塩基の沸点を高める観点で、ＲＮ１およびＲＮ２は炭素数５～１２のアルキル基が好ましい。ただし、金属（例えば銅）の層と積層する際の密着性を重視する処方においては、環状のアルキル基を有する基や炭素数１～８のアルキル基であることが好ましい。 As the aliphatic hydrocarbon group constituting RN1 and RN2 , a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain. Examples thereof include alkyl groups having. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. The linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group. Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
The group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
The alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later. However, in a formulation that emphasizes adhesion when laminated with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
　ＲＮ１およびＲＮ２は互いに連結して環状構造を形成していてもよい。環状構造を形成するにあたっては、酸素原子等を鎖中に有していてもよい。また、ＲＮ１およびＲＮ２が形成する環状構造は、単環であっても、縮合環であってもよいが、単環が好ましい。形成される環状構造としては、式（Ｎ１）中の窒素原子を含有する５員環または６員環が好ましく、例えば、ピロール環、イミダゾール環、ピラゾール環、ピロリン環、ピロリジン環、イミダゾリジン環、ピラゾリジン環、ピぺリジン環、ピペラジン環、モルホリン環などが挙げられ、ピロリン環、ピロリジン環、ピペリジン環、ピペラジン環、モルホリン環が好ましく挙げられる。 RN1 and RN2 may be connected to each other to form an annular structure. In forming the cyclic structure, oxygen atoms or the like may be contained in the chain. Further, the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable. As the cyclic structure to be formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like. Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.
　ＲＣ１は水素原子または保護基を表し、水素原子が好ましい。 RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
　保護基としては、酸または塩基の作用により分解する保護基が好ましく、酸で分解する保護基が好ましく挙げられる。 As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
　保護基の具体例としては、鎖状もしくは環状のアルキル基または鎖中に酸素原子を有する鎖状もしくは環状のアルキル基が挙げられる。鎖状もしくは環状のアルキル基としては、メチル基、エチル基、イソプロピル基、ｔｅｒｔ－ブチル基、シクロヘキシル基等が挙げられる。鎖中に酸素原子を有する鎖状のアルキル基としては、具体的にはアルキルオキシアルキル基が挙げられ、さらに具体的には、メチルオキシメチメチル（ＭＯＭ）基、エチルオキシエチル（ＥＥ）基等が挙げられる。鎖中に酸素原子を有する環状のアルキル基としては、エポキシ基、グリシジル基、オキセタニル基、テトラヒドロフラニル基、テトラヒドロピラニル（ＴＨＰ）基等が挙げられる。 Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethimethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
　Ｌを構成する２価の連結基としては、特に定めるものではないが、炭化水素基が好ましく、脂肪族炭化水素基がより好ましい。炭化水素基は、置換基を有していてもよく、また、炭化水素鎖の中に炭素原子以外の種類の原子を有していてもよい。より具体的には、鎖中に酸素原子を有していてもよい２価の炭化水素連結基であることが好ましく、鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基、２価の芳香族炭化水素基、または鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基と２価の芳香族炭化水素基の組み合わせに係る基がより好ましく、鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基がさらに好ましい。これらの基は、酸素原子を有していないほうが好ましい。
　２価の炭化水素連結基は、炭素数１～２４のものが好ましく、２～１２がより好ましく、２～６がさらに好ましい。２価の脂肪族炭化水素基は、炭素数１～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。２価の芳香族炭化水素基は、炭素数６～２２のものが好ましく、６～１８がより好ましく、６～１０がさらに好ましい。２価の脂肪族炭化水素基と２価の芳香族炭化水素基の組み合わせに係る基（例えば、アリーレンアルキル基）は、炭素数７～２２のものが好ましく、７～１８がより好ましく、７～１０がさらに好ましい。 The divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
　連結基Ｌとしては、具体的に、直鎖または分岐の鎖状アルキレン基、環状アルキレン基、鎖状アルキレン基と環状アルキレン基の組み合わせに係る基、酸素原子を鎖中に有しているアルキレン基、直鎖または分岐の鎖状のアルケニレン基、環状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましい。
　直鎖または分岐の鎖状アルキレン基は、炭素数１～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。
　環状アルキレン基は、炭素数３～１２のものが好ましく、３～６がより好ましい。
　鎖状アルキレン基と環状アルキレン基の組み合わせに係る基は、炭素数４～２４のものが好ましく、４～１２がより好ましく、４～６がさらに好ましい。
　酸素原子を鎖中に有するアルキレン基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。酸素原子を鎖中に有するアルキレン基は、炭素数１～１２のものが好ましく、１～６がより好ましく、１～３がさらに好ましい。 Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , A linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
　直鎖または分岐の鎖状のアルケニレン基は、炭素数２～１２のものが好ましく、２～６がより好ましく、２～３がさらに好ましい。直鎖または分岐の鎖状のアルケニレン基は、Ｃ＝Ｃ結合の数は１～１０のものが好ましく、１～６がより好ましく、１～３がさらに好ましい。
　環状のアルケニレン基は、炭素数３～１２のものが好ましく、３～６がより好ましい。環状のアルケニレン基は、Ｃ＝Ｃ結合の数は１～６が好ましく、１～４がより好ましく、１～２がさらに好ましい。
　アリーレン基は、炭素数６～２２のものが好ましく、６～１８がより好ましく、６～１０がさらに好ましい。
　アリーレンアルキレン基は、炭素数７～２３のものが好ましく、７～１９がより好ましく、７～１１がさらに好ましい。
　中でも、鎖状アルキレン基、環状アルキレン基、酸素原子を鎖中に有するアルキレン基、鎖状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましく、１，２－エチレン基、プロパンジイル基（特に１，３－プロパンジイル基）、シクロヘキサンジイル基（特に１，２－シクロヘキサンジイル基）、ビニレン基（特にシスビニレン基）、フェニレン基（１，２-フェニレン基）、フェニレンメチレン基（特に１，２－フェニレンメチレン基）、エチレンオキシエチレン基（特に１，２－エチレンオキシ－１，２－エチレン基）がより好ましい。 The linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched chain-like alkenylene group preferably has 1 to 10 C = C bonds, more preferably 1 to 6, and even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. For the cyclic alkenylene group, the number of C = C bonds is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
　塩基発生剤としては、下記の例が挙げられるが、本発明がこれにより限定して解釈されるものではない。 Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　非イオン型塩基発生剤の分子量は、８００以下であることが好ましく、６００以下であることがより好ましく、５００以下であることが更に好ましい。下限としては、１００以上であることが好ましく、２００以上であることがより好ましく、３００以上であることが更に好ましい。 The molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
　イオン型塩基発生剤の具体的な好ましい化合物としては、例えば、国際公開第２０１８／０３８００２号の段落番号０１４８～０１６３に記載の化合物も挙げられる。 Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
　アンモニウム塩の具体例としては、以下の化合物を挙げることができるが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000046
 Specific examples of the ammonium salt include, but are not limited to, the following compounds.
Figure JPOXMLDOC01-appb-C000046
　イミニウム塩の具体例としては、以下の化合物を挙げることができるが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000047
 Specific examples of the iminium salt include, but are not limited to, the following compounds.
Figure JPOXMLDOC01-appb-C000047
　本発明の樹脂組成物が塩基発生剤を含む場合、塩基発生剤の含有量は、本発明の樹脂組成物中の樹脂１００質量部に対し、０．１～５０質量部が好ましい。下限は、０．３質量部以上がより好ましく、０．５質量部以上が更に好ましい。上限は、３０質量部以下がより好ましく、２０質量部以下が更に好ましく、１０質量部以下が一層好ましく、５質量部以下であってもよく、４質量部以下であってもよい。
　塩基発生剤は、１種又は２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
As the base generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
＜重合性化合物＞
　本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
　重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include radical cross-linking agents and other cross-linking agents.
〔ラジカル架橋剤〕
　本発明の樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
　ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、（メタ）アクリロイル基、マレイミド基、（メタ）アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
　これらの中でも、上記エチレン性不飽和結合を含む基としては、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、（メタ）アクリロイル基がより好ましい。 [Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among these, as the group containing the ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
　ラジカル架橋剤は、エチレン性不飽和結合を１個以上有する化合物であることが好ましいが、２個以上有する化合物であることがより好ましい。ラジカル架橋剤は、エチレン性不飽和結合を３個以上有していてもよい。
　上記エチレン性不飽和結合を２個以上有する化合物としては、エチレン性不飽和結合を２～１５個有する化合物が好ましく、エチレン性不飽和結合を２～１０個有する化合物がより好ましく、２～６個有する化合物が更に好ましい。
　また、得られるパターン（硬化物）の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を２個有する化合物と、上記エチレン性不飽和結合を３個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical cross-linking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable. The compound having is more preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
　ラジカル架橋剤の分子量は、２，０００以下が好ましく、１，５００以下がより好ましく、９００以下が更に好ましい。ラジカル架橋剤の分子量の下限は、１００以上が好ましい。 The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
　ラジカル架橋剤の具体例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、及び不飽和カルボン酸と多価アミン化合物とのアミド類である。また、ヒドロキシ基やアミノ基、スルファニル基等の求核性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能イソシアネート類又はエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更に、ハロゲノ基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。具体例としては、特開２０１６－０２７３５７号公報の段落０１１３～０１２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polymorphic acid group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.
　また、ラジカル架橋剤は、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、（メタ）アクリレート化した化合物、特公昭４８－０４１７０８号公報、特公昭５０－００６０３４号公報、特開昭５１－０３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－０６４１８３号、特公昭４９－０４３１９１号、特公昭５２－０３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレート及びこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和結合を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。 Further, as the radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, which is described in JP-A-48-041708, JP-B-50-006034, and JP-A-51-037193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) described in JP-A-48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
　また、上述以外の好ましいラジカル架橋剤として、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号公報等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。 Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.
　更に、その他の例としては、特公昭４６－０４３９４６号公報、特公平０１－０４０３３７号公報、特公平０１－０４０３３６号公報に記載の特定の不飽和化合物や、特開平０２－０２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭６１－０２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。更に日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマー及びオリゴマーとして紹介されているものも使用することができる。 Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.
　上記のほか、特開２０１５－０３４９６４号公報の段落００４８～００５１に記載の化合物、国際公開第２０１５／１９９２１９号の段落００８７～０１３１に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.
　また、特開平１０－０６２９８６号公報において式（１）及び式（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、ラジカル架橋剤として用いることができる。 Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
　更に、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物もラジカル架橋剤として用いることができ、これらの内容は本明細書に組み込まれる。 Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.
　ラジカル架橋剤としては、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製、Ａ－ＴＭＭＴ：新中村化学工業（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ；新中村化学工業社製）、及びこれらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable. These oligomer types can also be used.
　ラジカル架橋剤の市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、２３１、２３９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（日本製紙社製）、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学工業社製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学社製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
　ラジカル架橋剤としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、ラジカル架橋剤として、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平０１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する化合物を用いることもできる。 Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
　ラジカル架橋剤は、カルボキシ基、リン酸基等の酸基を有するラジカル架橋剤であってもよい。酸基を有するラジカル架橋剤は、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤がより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤において、脂肪族ポリヒドロキシ化合物がペンタエリスリトール又はジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成（株）製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。 The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The radical cross-linking agent provided with the above is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
　酸基を有するラジカル架橋剤の好ましい酸価は、０．１～３００ｍｇＫＯＨ／ｇであり、特に好ましくは１～１００ｍｇＫＯＨ／ｇである。ラジカル架橋剤の酸価が上記範囲であれば、製造上の取扱性に優れ、更には、現像性に優れる。また、重合性が良好である。上記酸価は、ＪＩＳ　Ｋ　００７０：１９９２の記載に準拠して測定される。 The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. The acid value is measured according to the description of JIS K 0070: 1992.
　樹脂組成物は、パターンの解像性と膜の伸縮性の観点から、２官能のメタアクリレート又はアクリレートを用いることが好ましい。
　具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、ＰＥＧ（ポリエチレングリコール）２００ジアクリレート、ＰＥＧ２００ジメタクリレート、ＰＥＧ６００ジアクリレート、ＰＥＧ６００ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、３－メチル-１，５-ペンタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，６ヘキサンジオールジメタクリレート、ジメチロール－トリシクロデカンジアクリレート、ジメチロール－トリシクロデカンジメタクリレート、ビスフェノールＡのＥＯ（エチレンオキシド）付加物ジアクリレート、ビスフェノールＡのＥＯ付加物ジメタリレート、ビスフェノールＡのＰＯ（プロピレンオキシド）付加物ジアクリレート、ビスフェノールＡのＥＯ付加物ジメタリレート、２－ヒドロキシー３－アクリロイロキシプロピルメタクリレート、イソシアヌル酸ＥＯ変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する２官能アクリレート、ウレタン結合を有する２官能メタクリレートを使用することができる。これらは必要に応じ、２種以上を混合し使用することができる。
　なお、例えばＰＥＧ２００ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が２００程度のものをいう。
　本発明の樹脂組成物は、パターン（硬化物）の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。
　その他、２官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。 As the resin composition, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 dimethacrylate. Methacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate, 3-Methyl-1,5-Pentanediol Diacrylate, 1,6-Hexanediol Diacrylate, 1,6 hexanediol dimethacrylate, dimethyrole-tricyclodecanediacrylate, dimethyrole-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethalilate of bisphenol A, PO (propylene) of bisphenol A Oxide) Additive Diacrylate, EO Additive Dimetalylate of Bisphenol A, 2-Hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate with urethane bond, urethane bond Bifunctional methacrylate having the above can be used. If necessary, two or more of these can be mixed and used.
For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product). Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other examples of the bifunctional or higher functional cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
　ラジカル架橋剤を含有する場合、その含有量は、本発明の樹脂組成物の全固形分に対して、０質量％超６０質量％以下であることが好ましい。下限は５質量％以上がより好ましい。上限は、５０質量％以下であることがより好ましく、３０質量％以下であることが更に好ましい。 When a radical cross-linking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
　ラジカル架橋剤は１種を単独で用いてもよいが、２種以上を混合して用いてもよい。２種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.
〔他の架橋剤〕
　本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
　本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
　上記酸は、露光工程において、光酸発生剤から発生する酸であることが好ましい。
　他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
　他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
　上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
　これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも１種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも１種の化合物を含むことがより好ましい。 [Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator. A compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof. A compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
The acid is preferably an acid generated from a photoacid generator in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group. A compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group. Examples thereof include compounds having a structure substituted with an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
　本発明におけるアルコキシメチル基及びアシルオキシメチル基の少なくとも１つを含有する化合物としては、アルコキシメチル基又はアシルオキシメチル基が、直接芳香族基や下記ウレア構造の窒素原子上に、又は、トリアジン上に置換した化合物を構造例として挙げることができる。
　上記化合物が有するアルコキシメチル基又はアシルオキシメチル基は、炭素数２～５が好ましく、炭素数２又は３が好ましく、炭素数２がより好ましい。
　上記化合物が有するアルコキシメチル基及びアシルオキシメチル基の総数は１～１０が好ましく、より好ましくは２～８、特に好ましくは３～６である。
　上記化合物の分子量は好ましくは１５００以下であり、１８０～１２００が好ましい。 As the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group in the present invention, the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom of the following urea structure, or on triazine. Can be mentioned as a structural example.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　Ｒ１００は、アルキル基又はアシル基を表す。
　Ｒ１０１及びＲ１０２は、それぞれ独立に、一価の有機基を表し、互いに結合して環を形成してもよい。 R 100 represents an alkyl group or an acyl group.
R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
　アルコキシメチル基又はアシルオキシメチル基が直接芳香族基に置換した化合物としては、例えば下記一般式の様な化合物を挙げることができる。 Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　式中、Ｘは単結合又は２価の有機基を示し、個々のＲ１０４はそれぞれ独立にアルキル基又はアシル基を示し、Ｒ１０３は、水素原子、アルキル基、アルケニル基、アリール基、アラルキル基、又は、酸の作用により分解し、アルカリ可溶性基を生じる基（例えば、酸の作用により脱離する基、－Ｃ（Ｒ４）２ＣＯＯＲ５で表される基（Ｒ４はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表し、Ｒ５は酸の作用により脱離する基を表す。））を示す。
　Ｒ１０５は各々独立にアルキル基又はアルケニル基を示し、ａ、ｂ及びｃは各々独立に１～３であり、ｄは０～４であり、ｅは０～３であり、ｆは０～３であり、ａ＋ｄは５以下であり、ｂ＋ｅは４以下であり、ｃ＋ｆは４以下である。
　酸の作用により分解し、アルカリ可溶性基を生じる基、酸の作用により脱離する基、－Ｃ（Ｒ４）２ＣＯＯＲ５で表される基におけるＲ５については、例えば、－Ｃ（Ｒ３６）（Ｒ３７）（Ｒ３８）、－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３９）、－Ｃ（Ｒ０１）（Ｒ０２）（ＯＲ３９）等を挙げることができる。
　式中、Ｒ３６～Ｒ３９は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。Ｒ３６とＲ３７とは、互いに結合して環を形成してもよい。
　上記アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～５のアルキル基がより好ましい。
　上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
　上記シクロアルキル基としては、炭素数３～１２のシクロアルキル基が好ましく、炭素数３～８のシクロアルキル基がより好ましい。
　上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
　上記アリール基は炭素数６～３０の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
　上記アラルキル基としては、炭素数７～２０のアラルキル基が好ましく、炭素数７～１６のアラルキル基がより好ましい。
　上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
　上記アルケニル基は炭素数３～２０のアルケニル基が好ましく、炭素数３～１６のアルケニル基がより好ましい。
　また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。 In the formula, X represents a single-bonded or divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group. , Or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C (R 4 ) 2 COOR 5 (R 4 is independent, respectively, It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group desorbed by the action of an acid.))).
R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
For R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ). ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), -C (R 01 ) (R 02 ) (OR 39 ) and the like.
In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be coupled to each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
　Ｒ０１及びＲ０２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
　これらの基としては好ましくは、第３級アルキルエステル基、アセタールエステル基、クミルエステル基、エノールエステル基等である。更に好ましくは、第３級アルキルエステル基、アセタールエステル基である。 These groups are preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group and the like. More preferably, it is a tertiary alkyl ester group or an acetal ester group.
　アルコキシメチル基を有する化合物としては具体的に以下の構造を挙げることができる。アシルオキシメチル基を有する化合物は下記化合物のアルコキシメチル基をアシルオキシメチル基に変更した化合物を挙げることができる。アルコキシメチル基又はアシルオキシメチルを分子内に有する化合物としては以下の様な化合物を挙げることができるが、これらに限定されるものではない。 Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　アルコキシメチル基及びアシルオキシメチル基の少なくとも１つを含有する化合物は、市販のものを用いても、公知の方法により合成したものを用いてもよい。
　耐熱性の観点で、アルコキシメチル基又はアシルオキシメチル基が、直接芳香環やトリアジン環上に置換した化合物が好ましい。 As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
　メラミン系架橋剤の具体例としては、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシブチルメラミンなどが挙げられる。 Specific examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
　尿素系架橋剤の具体例としては、例えば、モノヒドロキシメチル化グリコールウリル、ジヒドロキシメチル化グリコールウリル、トリヒドロキシメチル化グリコールウリル、テトラヒドロキシメチル化グリコールウリル、モノメトキシメチル化グリコールウリル，ジメトキシメチル化グリコールウリル、トリメトキシメチル化グリコールウリル、テトラメトキシメチル化グリコールウリル、モノメトキシメチル化グリコールウリル、ジメトキシメチル化グリコールウリル、トリメトキシメチル化グリコールウリル、テトラエトキシメチル化グリコールウリル、モノプロポキシメチル化グリコールウリル、ジプロポキシメチル化グリコールウリル、トリプロポキシメチル化グリコールウリル、テトラプロポキシメチル化グリコールウリル、モノブトキシメチル化グリコールウリル、ジブトキシメチル化グリコールウリル、トリブトキシメチル化グリコールウリル、又は、テトラブトキシメチル化グリコールウリルなどのグリコールウリル系架橋剤；ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、１，３－ジ（メトキシメチル）４，５－ジヒドロキシ－２－イミダゾリジノン、１，３－ジ（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl Glycol-based cross-linking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea and other urea-based cross-linking agents, monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethyl Ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene Propropylene urea-based cross-linking agents such as urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea, 1,3-di (methoxymethyl) 4, Examples thereof include 5-dihydroxy-2-imidazolidinone, 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
　ベンゾグアナミン系架橋剤の具体例としては、例えばモノヒドロキシメチル化ベンゾグアナミン、ジヒドロキシメチル化ベンゾグアナミン、トリヒドロキシメチル化ベンゾグアナミン、テトラヒドロキシメチル化ベンゾグアナミン、モノメトキシメチル化ベンゾグアナミン、ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラメトキシメチル化ベンゾグアナミン、モノメトキシメチル化ベンゾグアナミン、ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラエトキシメチル化ベンゾグアナミン、モノプロポキシメチル化ベンゾグアナミン、ジプロポキシメチル化ベンゾグアナミン、トリプロポキシメチル化ベンゾグアナミン、テトラプロポキシメチル化ベンゾグアナミン、モノブトキシメチル化ベンゾグアナミン、ジブトキシメチル化ベンゾグアナミン、トリブトキシメチル化ベンゾグアナミン、テトラブトキシメチル化ベンゾグアナミンなどが挙げられる。 Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
　その他、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基を有する化合物としては、芳香環（好ましくはベンゼン環）にメチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基が直接結合した化合物も好適に用いられる。
　このような化合物の具体例としては、ベンゼンジメタノール、ビス（ヒドロキシメチル）クレゾール、ビス（ヒドロキシメチル）ジメトキシベンゼン、ビス（ヒドロキシメチル）ジフェニルエーテル、ビス（ヒドロキシメチル）ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス（ヒドロキシメチル）ビフェニル、ジメチルビス（ヒドロキシメチル）ビフェニル、ビス（メトキシメチル）ベンゼン、ビス（メトキシメチル）クレゾール、ビス（メトキシメチル）ジメトキシベンゼン、ビス（メトキシメチル）ジフェニルエーテル、ビス（メトキシメチル）ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス（メトキシメチル）ビフェニル、ジメチルビス（メトキシメチル）ビフェニル、４，４’，４’’－エチリデントリス［２，６－ビス（メトキシメチル）フェノール］、５，５’－［２，２，２‐トリフルオロ‐１‐（トリフルオロメチル）エチリデン］ビス［２‐ヒドロキシ‐１，３‐ベンゼンジメタノール］、３，３’，５，５’－テトラキス（メトキシメチル）－１，１’－ビフェニル－４，４’－ジオール等が挙げられる。 In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the group of the species is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.
　他の架橋剤としては市販品を用いてもよく、好適な市販品としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、旭有機材工業社製）、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＥＰ、ＤＭＬ－ＯＣ、ＤＭＬ－ＯＥＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＰＯＰ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＴｒｉｓＰＣ、ＤＭＬ－ＢｉｓＯＣ－Ｚ、ＤＭＬ－ＢｉｓＯＣＨＰ－Ｚ、ＤＭＬ－ＢＰＣ、ＤＭＬＢｉｓＯＣ－Ｐ、ＤＭＯＭ－ＰＣ、ＤＭＯＭ－ＰＴＢＰ、ＤＭＯＭ－ＭＢＰＣ、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＨＱ、ＴＭＬ－ＢＰ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＥ、ＴＭＬ－ＢＰＡ、ＴＭＬ－ＢＰＡＦ、ＴＭＬ－ＢＰＡＰ、ＴＭＯＭ－ＢＰ、ＴＭＯＭ－ＢＰＥ、ＴＭＯＭ－ＢＰＡ、ＴＭＯＭ－ＢＰＡＦ、ＴＭＯＭ－ＢＰＡＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ、ＨＭＯＭ－ＴＰＰＨＢＡ、ＨＭＯＭ－ＴＰＨＡＰ（以上、本州化学工業社製）、ニカラック（登録商標、以下同様）ＭＸ－２９０、ニカラックＭＸ－２８０、ニカラックＭＸ－２７０、ニカラックＭＸ－２７９、ニカラックＭＷ－１００ＬＭ、ニカラックＭＸ－７５０ＬＭ（以上、三和ケミカル社製）などが挙げられる。 Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.
　また、本発明の樹脂組成物は、他の架橋剤として、エポキシ化合物、オキセタン化合物、及び、ベンゾオキサジン化合物よりなる群から選ばれた少なくとも１種の化合物を含むことも好ましい。 Further, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
－エポキシ化合物（エポキシ基を有する化合物）－
　エポキシ化合物としては、一分子中にエポキシ基を２以上有する化合物であることが好ましい。エポキシ基は、２００℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。 -Epoxy compound (compound having an epoxy group)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
　エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの繰返し単位数が２以上のものを意味し、繰返し単位数が２～１５であることが好ましい。 The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ブチレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等のアルキレングリコール型エポキシ樹脂又は多価アルコール炭化水素型エポキシ樹脂；ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８３０ＬＶＰ、エピクロン（登録商標）ＥＸＡ－８１８３、エピクロン（登録商標）ＥＸＡ－８１６９、エピクロン（登録商標）Ｎ－６６０、エピクロン（登録商標）Ｎ－６６５－ＥＸＰ－Ｓ、エピクロン（登録商標）Ｎ－７４０（以上商品名、ＤＩＣ（株）製）、リカレジン（登録商標）ＢＥＯ－２０Ｅ、リカレジン（登録商標）ＢＥＯ－６０Ｅ、リカレジン（登録商標）ＨＢＥ－１００、リカレジン（登録商標）ＤＭＥ－１００、リカレジン（登録商標）Ｌ－２００（商品名、新日本理化（株））、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ、ＥＰ－４０８８Ｓ、ＥＰ－３９５０Ｓ（以上商品名、（株）ＡＤＥＫＡ製）、セロキサイド（登録商標）２０２１Ｐ、セロキサイド（登録商標）２０８１、セロキサイド（登録商標）２０００、ＥＨＰＥ３１５０、エポリード（登録商標）ＧＴ４０１、エポリード（登録商標）ＰＢ４７００、エポリード（登録商標）ＰＢ３６００（以上商品名、（株）ダイセル製）、ＮＣ－３０００、ＮＣ－３０００－Ｌ、ＮＣ－３０００－Ｈ、ＮＣ－３０００－ＦＨ－７５Ｍ、ＮＣ－３１００、ＣＥＲ－３０００－Ｌ、ＮＣ－２０００－Ｌ、ＸＤ－１０００、ＮＣ－７０００Ｌ、ＮＣ－７３００Ｌ、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＣＥＲ－１０２０、ＥＰＰＮ－２０１、ＢＲＥＮ－Ｓ、ＢＲＥＮ－１０Ｓ（以上商品名、日本化薬（株）製）などが挙げられる。また以下の化合物も好適に用いられる。 Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® HP-4770, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron® EXA-8169, Epicron® N-660, Epicron® N-665-EXP-S, Epicron (registered trademark) N-740 (trademark, manufactured by DIC Co., Ltd.), Ricaresin (registered trademark) BEO-20E, Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S ( Product names, ADEKA Co., Ltd., celoxide (registered trademark) 2021P, celoxide (registered trademark) 2081, celoxide (registered trademark) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide ( Registered trademark) PB3600 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. The following compounds are also preferably used.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　式中ｎは１～５の整数、ｍは１～２０の整数である。 In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.
　上記構造の中でも、耐熱性と伸度向上を両立する点から、ｎは１～２、ｍは３～７であることが好ましい。 Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
－オキセタン化合物（オキセタニル基を有する化合物）－
　オキセタン化合物としては、一分子中にオキセタン環を２つ以上有する化合物、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシルメチル）オキセタン、１，４－ベンゼンジカルボン酸－ビス［（３－エチル－３－オキセタニル）メチル］エステル等を挙げることができる。具体的な例としては、東亞合成（株）製のアロンオキセタンシリーズ（例えば、ＯＸＴ－１２１、ＯＸＴ－２２１）が好適に使用することができ、これらは単独で、又は２種以上混合してもよい。 -Oxetane compound (compound having an oxetanyl group)-
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
－ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物）－
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 -Benzoxazine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
　ベンゾオキサジン化合物の好ましい例としては、Ｐ－ｄ型ベンゾオキサジン、Ｆ－ａ型ベンゾオキサジン（以上、商品名、四国化成工業社製）、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、又は２種以上混合してもよい。 Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo. Examples include oxazine compounds. These may be used alone or in combination of two or more.
　他の架橋剤の含有量は、本発明の樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、０．１～２０質量％であることがより好ましく、０．５～１５質量％であることが更に好ましく、１．０～１０質量％であることが特に好ましい。他の架橋剤は１種のみ含有していてもよいし、２種以上含有していてもよい。他の架橋剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
＜金属接着性改良剤＞
　本発明の樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等などが挙げられる。 <Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a β-ketoester. Examples thereof include compounds and amino compounds.
〔シランカップリング剤〕
　シランカップリング剤としては、例えば、国際公開第２０１５／１９９２１９号の段落０１６７に記載の化合物、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開第２０１１／０８０９９２号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－０４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開第２０１４／０９７５９４号の段落００５５に記載の化合物、特開２０１８－１７３５７３の段落００６７～００７８に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｍｅはメチル基を、Ｅｔはエチル基を表す。 〔Silane coupling agent〕
Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　他のシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、トリス－（トリメトキシシリルプロピル）イソシアヌレート、３－ウレイドプロピルトリアルコキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－トリメトキシシリルプロピルコハク酸無水物が挙げられる。これらは１種単独または２種以上を組み合わせて使用することができる。 Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples thereof include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
〔アルミニウム系接着助剤〕
　アルミニウム系接着助剤としては、例えば、アルミニウムトリス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトネート）、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
　また、その他の金属接着性改良剤としては、特開２０１４－１８６１８６号公報の段落００４６～００４９に記載の化合物、特開２０１３－０７２９３５号公報の段落００３２～００４３に記載のスルフィド系化合物を用いることもでき、これらの内容は本明細書に組み込まれる。 As other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 are used. These may also be incorporated herein by reference.
　金属接着性改良剤の含有量は特定樹脂１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．０１～１０質量部の範囲であり、更に好ましくは０．５～５質量部の範囲である。上記下限値以上とすることでパターンと金属層との接着性が良好となり、上記上限値以下とすることでパターンの耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.
＜マイグレーション抑制剤＞
　本発明の樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層（金属配線）由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
　マイグレーション抑制剤としては、特に制限はないが、複素環（ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、２Ｈ－ピラン環及び６Ｈ－ピラン環、トリアジン環）を有する化合物、チオ尿素類及びスルファニル基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、１，２，４－トリアゾール、ベンゾトリアゾール、３－アミノ－１，２，４－トリアゾール、３，５－ジアミノ－１，２，４－トリアゾール等のトリアゾール系化合物、１Ｈ－テトラゾール、５－フェニルテトラゾール、５－アミノ―１Ｈ－テトラゾール等のテトラゾール系化合物が好ましく使用できる。 The migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenolic compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
　又はハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Alternatively, an ion trap agent that traps anions such as halogen ions can also be used.
　その他のマイグレーション抑制剤としては、特開２０１３－０１５７０１号公報の段落００９４に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－０５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６及び０１１８に記載の化合物、国際公開第２０１５／１９９２１９号の段落０１６６に記載の化合物などを使用することができ、これらの内容は本明細書に組み込まれる。 Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.
　マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。 Specific examples of the migration inhibitor include the following compounds.
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　本発明の樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、本発明の樹脂組成物の全固形分に対して、０．０１～５．０質量％であることが好ましく、０．０５～２．０質量％であることがより好ましく、０．１～１．０質量％であることが更に好ましい。 When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
　マイグレーション抑制剤は１種のみでもよいし、２種以上であってもよい。マイグレーション抑制剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 The migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
＜重合禁止剤＞
　本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、Ｎ－オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。 <Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
　重合禁止剤の具体的な化合物としては、ｐ－ヒドロキノン、ｏ－ヒドロキノン、ｏ－メトキシフェノール、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、１，４－ベンゾキノン、ジフェニル－ｐ－ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン第一セリウム塩、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルホプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、４‐ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、フェノチアジン、フェノキサジン、１，１－ジフェニル－２－ピクリルヒドラジル、ジブチルジチオカーバネート銅（ＩＩ）、ニトロベンゼン、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアルミニウム塩、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアンモニウム塩、などが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、及び、国際公開第２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N) -Sulfospropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane, 1,3,5-tris (4-) t-Butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2,2,6 6-Tetramethylpiperidine 1-oxyl-free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl-free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate Copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
　本発明の樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の樹脂組成物の全固形分に対して、０．０１～２０質量％であることが好ましく、０．０２～１５質量％であることがより好ましく、０．０５～１０質量％であることが更に好ましい。 When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
＜その他の添加剤＞
　本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、界面活性剤、高級脂肪酸誘導体、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類（例えば、消泡剤、難燃剤など）等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の樹脂組成物の固形分の３質量％以下とすることが好ましい。 <Other additives>
The resin composition of the present invention can be used with various additives such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, and oxidations, if necessary, to the extent that the effects of the present invention can be obtained. Inhibitors, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardant agents, etc.) can be blended. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
〔界面活性剤〕
　界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、炭化水素系界面活性剤などの各種界面活性剤を使用できる。界面活性剤はノニオン型界面活性剤であってもよく、カチオン型界面活性剤であってもよく、アニオン型界面活性剤であってもよい。 [Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
　本発明の感光性樹脂組成物に界面活性剤を含有させることで、塗布液として調製したときの液特性（特に、流動性）がより向上し、塗布厚の均一性や省液性をより改善することができる。即ち、界面活性剤を含有する組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力が低下して、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、厚みムラの小さい均一厚の膜形成をより好適に行うことができる。 By containing a surfactant in the photosensitive resin composition of the present invention, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、ＲＳ－７２－Ｋ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１、ノベックＦＣ４４３０、同ＦＣ４４３２（以上、スリーエム　ジャパン（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落００１５～０１５８に記載の化合物、特開２０１１－１３２５０３号公報の段落０１１７～０１３２に記載の化合物を用いることもでき、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤としてブロックポリマーを用いることもでき、具体例としては、例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。
　フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000055
 Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171, Novek FC4430, FC4432 (above, manufactured by 3M Japan Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.) ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000055
　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、５，０００～３０，０００であることがより好ましい。
　フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落００５０～００９０および段落０２８９～０２９５に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、市販品としては、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ等が挙げられる。 The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
　シリコーン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ３４１、ＫＦ６００１、ＫＦ６００２（以上、信越シリコーン（株）製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー（株）製）等が挙げられる。 Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
　炭化水素系界面活性剤としては、例えば、パイオニンＡ－７６、ニューカルゲンＦＳ－３ＰＧ、パイオニンＢ－７０９、パイオニンＢ－８１１－Ｎ、パイオニンＤ－１００４、パイオニンＤ－３１０４、パイオニンＤ－３６０５、パイオニンＤ－６１１２、パイオニンＤ－２１０４－Ｄ、パイオニンＤ－２１２、パイオニンＤ－９３１、パイオニンＤ－９４１、パイオニンＤ－９５１、パイオニンＥ－５３１０、パイオニンＰ－１０５０－Ｂ、パイオニンＰ－１０２８－Ｐ、パイオニンＰ－４０５０－Ｔ等（以上、竹本油脂社製）、などが挙げられる。 Examples of the hydrocarbon-based surfactant include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.
　ノニオン型界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステルなどが例示される。市販品としては、プルロニック（登録商標）Ｌ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000. (Manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil and Fat (Takemoto Oil & Fat) Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Kagaku Kogyo Co., Ltd.) and the like.
　カチオン型界面活性剤として具体的には、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．７７、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Specifically, as a cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.
　アニオン型界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）製）、サンデットＢＬ（三洋化成（株）製）等が挙げられる。 Specific examples of the anion-type surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
　界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
界面活性剤の含有量は、組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。 Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
〔高級脂肪酸誘導体〕
　本発明の樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で本発明の樹脂組成物の表面に偏在させてもよい。 [Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
　また、高級脂肪酸誘導体は、国際公開第２０１５／１９９２１９号の段落０１５５に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is incorporated in the present specification.
　本発明の樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましい。高級脂肪酸誘導体は１種のみでもよいし、２種以上であってもよい。高級脂肪酸誘導体が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
〔無機粒子〕
　本発明の樹脂組成物は、無機微粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
The resin composition of the present invention may contain inorganic fine particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
　上記無機粒子の平均粒子径としては、０．０１～２．０μｍが好ましく、０．０２～１．５μｍがより好ましく、０．０３～１．０μｍがさらに好ましく、０．０４～０．５μｍが特に好ましい。
　微粒子の上記平均粒子径は、一次粒子径であり、また体積平均粒子径である。体積平均粒子径は、Ｎａｎｏｔｒａｃ ＷＡＶＥ　ＩＩ ＥＸ－１５０（日機装社製）による動的光散乱法で測定できる。
上記測定が困難である場合は、遠心沈降光透過法、Ｘ線透過法、レーザー回折・散乱法で測定することもできる。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
The average particle size of the fine particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
〔紫外線吸収剤〕
　本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
　サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、ｐ－オクチルフェニルサリシレート、ｐ－ｔ－ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－アミル－５’－イソブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－イソブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－イソブチル－５’－プロピルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（１，１，３，３－テトラメチル）フェニル］ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
　置換アクリロニトリル系紫外線吸収剤の例としては、２－シアノ－３，３－ジフェニルアクリル酸エチル、２－シアノ－３，３－ジフェニルアクリル酸２－エチルヘキシルなどが挙げられる。さらに、トリアジン系紫外線吸収剤の例としては、２－［４－［（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－［４－［（２－ヒドロキシ－３－トリデシルオキシプロピル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（２，４－ジヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジンなどのモノ（ヒドロキシフェニル）トリアジン化合物；２，４－ビス（２－ヒドロキシ－４－プロピルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－３－メチル－４－プロピルオキシフェニル）－６－（４－メチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－３－メチル－４－ヘキシルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジンなどのビス（ヒドロキシフェニル）トリアジン化合物；２，４－ビス（２－ヒドロキシ－４－ブトキシフェニル）－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン、２，４，６－トリス（２－ヒドロキシ－４－オクチルオキシフェニル）－１，３，５－トリアジン、２，４，６－トリス［２－ヒドロキシ－４－（３－ブトキシ－２－ヒドロキシプロピルオキシ）フェニル］－１，３，５－トリアジンなどのトリス（ヒドロキシフェニル）トリアジン化合物等が挙げられる。 Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, as an example of the triazine-based ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-Triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) ) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.
　本発明においては、上記各種の紫外線吸収剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、０．００１質量％以上１質量％以下であることが好ましく、０．０１質量％以上０．１質量％以下であることがより好ましい。 In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
〔有機チタン化合物〕
　本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
　使用可能な有機チタン化合物としては、チタン原子に有機基が共有結合又はイオン結合を介して結合しているものが挙げられる。
　有機チタン化合物の具体例を、以下のＩ）～ＶＩＩ）に示す：
　Ｉ）チタンキレート化合物：中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を２個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス（トリエタノールアミン）ジイソプロポキサイド、チタニウムジ（ｎ－ブトキサイド）ビス（２，４－ペンタンジオネート、チタニウムジイソプロポキサイドビス（２，４－ペンタンジオネート）、チタニウムジイソプロポキサイドビス（テトラメチルヘプタンジオネート）、チタニウムジイソプロポキサイドビス（エチルアセトアセテート）等である。
　ＩＩ）テトラアルコキシチタン化合物：例えば、チタニウムテトラ（ｎ－ブトキサイド）、チタニウムテトラエトキサイド、チタニウムテトラ（２－エチルヘキソキサイド）、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ（ｎ－ノニロキサイド）、チタニウムテトラ（ｎ－プロポキサイド）、チタニウムテトラステアリロキサイド、チタニウムテトラキス［ビス｛２，２－（アリロキシメチル）ブトキサイド｝］等である。
　ＩＩＩ）チタノセン化合物：例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロフェニル）チタニウム、ビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム等である。
　ＩＶ）モノアルコキシチタン化合物：例えば、チタニウムトリス（ジオクチルホスフェート）イソプロポキサイド、チタニウムトリス（ドデシルベンゼンスルホネート）イソプロポキサイド等である。
　Ｖ）チタニウムオキサイド化合物：例えば、チタニウムオキサイドビス（ペンタンジオネート）、チタニウムオキサイドビス（テトラメチルヘプタンジオネート）、フタロシアニンチタニウムオキサイド等である。
　ＶＩ）チタニウムテトラアセチルアセトネート化合物：例えば、チタニウムテトラアセチルアセトネート等である。
　ＶＩＩ）チタネートカップリング剤：例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
　中でも、有機チタン化合物としては、上記Ｉ）チタンキレート化合物、ＩＩ）テトラアルコキシチタン化合物、及びＩＩＩ）チタノセン化合物から成る群から選ばれる少なくとも１種の化合物であることが、より良好な耐薬品性を奏するという観点から好ましい。特に、チタニウムジイソプロポキサイドビス（エチルアセトアセテート）、チタニウムテトラ（ｎ－ブトキサイド）、及びビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウムが好ましい。 Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.
　有機チタン化合物を配合する場合、その配合量は、特定樹脂１００質量部に対し、０．０５～１０質量部であることが好ましく、より好ましくは０．１～２質量部である。配合量が０．０５質量部以上である場合、得られる硬化パターンに良好な耐熱性及び耐薬品性がより効果的に発現し、一方１０質量部以下である場合、組成物の保存安定性により優れる。 When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
〔酸化防止剤〕
　本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。上述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第２０１４／０２１０２３号、国際公開第２０１７／０３０００５号、特開２０１７－００８２１９号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。
　好ましい酸化防止剤の例としては、２，２－チオビス（４－メチル－６－ｔ－ブチルフェノール）、２，６－ジ－ｔ－ブチルフェノールおよび式（３）で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　一般式（３）中、Ｒ５は水素原子または炭素数２以上（好ましくは炭素数２～１０）のアルキル基を表し、Ｒ６は炭素数２以上（好ましくは炭素数２～１０）のアルキレン基を表す。Ｒ７は、炭素数２以上（好ましくは炭素数２～１０）のアルキレン基、酸素原子、および窒素原子のうち少なくともいずれかを含む１～４価の有機基を示す。ｋは１～４の整数を示す。 In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group. R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.
　式（３）で表される化合物は、樹脂が有する脂肪族基やフェノール性水酸基の酸化劣化を抑制する。また、金属材料への防錆作用により、金属酸化を抑制することができる。 The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.
　樹脂と金属材料に同時に作用できるため、ｋは２～４の整数がより好ましい。Ｒ７としては、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシル基、カルボニル基、アリル基、ビニル基、複素環基、－Ｏ－、－ＮＨ－、－ＮＨＮＨ－、それらを組み合わせたものなどが挙げられ、さらに置換基を有していてもよい。この中でも、現像液への溶解性や金属密着性の点から、アルキルエーテル基、－ＮＨ－を有することが好ましく、樹脂との相互作用と金属錯形成による金属密着性の点から－ＮＨ－がより好ましい。 Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have an alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
　一般式（３）で表される化合物は、例としては以下のものが挙げられるが、下記構造に限らない。 Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　酸化防止剤の添加量は、樹脂に対し、０．１～１０質量部が好ましく、０．５～５質量部がより好ましい。添加量を０．１質量部以上とすることにより、高温高湿環境下においても伸度特性や金属材料に対する密着性向上の効果が得られやすく、また１０質量部以下とすることにより、例えば感光剤との相互作用により、樹脂組成物の感度が向上する。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. When the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, photosensitive is exhibited. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
〔凝集防止剤〕
　本実施形態の樹脂組成物は、必要に応じて凝集防止剤を含有してもよい。凝集防止剤としては、ポリアクリル酸ナトリウム等が挙げられる。 [Anti-coagulation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the antiaggregating agent include sodium polyacrylate and the like.
　本発明においては、凝集防止剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上１０質量％以下であることが好ましく、０．０２質量％以上５質量％以下であることがより好ましい。 In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
〔フェノール系化合物〕
　本実施形態の樹脂組成物は、必要に応じてフェノール系化合物を含有してもよい。フェノール系化合物としては、Ｂｉｓ－Ｚ、ＢｉｓＰ－ＥＺ、ＴｅｋＰ－４ＨＢＰＡ、ＴｒｉｓＰ－ＨＡＰ、ＴｒｉｓＰ－ＰＡ、ＢｉｓＯＣＨＰ－Ｚ、ＢｉｓＰ－ＭＺ、ＢｉｓＰ－ＰＺ、ＢｉｓＰ－ＩＰＺ、ＢｉｓＯＣＰ－ＩＰＺ、ＢｉｓＰ－ＣＰ、ＢｉｓＲＳ－２Ｐ、ＢｉｓＲＳ－３Ｐ、ＢｉｓＰ－ＯＣＨＰ、メチレントリス－ＦＲ－ＣＲ、ＢｉｓＲＳ－２６Ｘ（以上、商品名、本州化学工業（株）製）、ＢＩＰ－ＰＣ、ＢＩＲ－ＰＣ、ＢＩＲ－ＰＴＢＰ、ＢＩＲ－ＢＩＰＣ－Ｆ（以上、商品名、旭有機材工業（株）製）等が挙げられる。 [Phenolic compounds]
The resin composition of the present embodiment may contain a phenolic compound, if necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP. BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.
　本発明においては、フェノール系化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上３０質量％以下であることが好ましく、０．０２質量％以上２０質量％以下であることがより好ましい。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
〔他の高分子化合物〕
　他の高分子化合物としては、シロキサン樹脂、（メタ）アクリル酸を共重合した（メタ）アクリルポリマー、ノボラック樹脂、レゾール樹脂、ポリヒドロキシスチレン樹脂およびそれらの共重合体などが挙げられる。他の高分子化合物はメチロール基、アルコキシメチル基、エポキシ基などの架橋基が導入された変性体であってもよい。 [Other polymer compounds]
Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
　本発明においては、他の高分子化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上３０質量％以下であることが好ましく、０．０２質量％以上２０質量％以下であることがより好ましい。 In the present invention, one type of other polymer compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
＜樹脂組成物の特性＞
　本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、１，０００ｍｍ２／ｓ～１２，０００ｍｍ２／ｓが好ましく、２，０００ｍｍ２／ｓ～１０，０００ｍｍ２／ｓがより好ましく、３，０００ｍｍ２／ｓ～８，０００ｍｍ２／ｓが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。１,０００ｍｍ２／s以下では、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが困難であり、１２,０００ｍｍ２／s以上では、塗布面状が悪化する可能性がある。 <Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 3,000 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film. At 1,000 mm 2 / s or less, it is difficult to apply the film with a film thickness required as an insulating film for rewiring, for example, and at 12,000 mm 2 / s or more, the coating surface condition may deteriorate. ..
＜樹脂組成物の含有物質についての制限＞
　本発明の樹脂組成物の含水率は、２．０質量％未満であることが好ましく、１．５質量％未満であることがより好ましく、１．０質量％未満であることが更に好ましい。２．０％以上では、樹脂組成物の保存安定性が損なわれる可能性がある。
　水分の含有量を維持する方法としては、保管条件における湿度の調整、保管時の収容容器の空隙率低減などが挙げられる。 <Restrictions on substances contained in the resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired.
Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
　本発明の樹脂組成物の金属含有量は、絶縁性の観点から、５質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満が更に好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、銅、クロム、ニッケルなどが挙げられるが、有機化合物と金属との錯体として含まれる金属は除く。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。 The metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
　また、本発明の樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の樹脂組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフルオロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 Further, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention. Examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
　本発明の樹脂組成物は、半導体材料としての用途を考慮すると、ハロゲン原子の含有量が、配線腐食性の観点から、５００質量ｐｐｍ未満が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満が更に好ましい。中でも、ハロゲンイオンの状態で存在するものは、５質量ｐｐｍ未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満が更に好ましい。ハロゲン原子としては、塩素原子及び臭素原子が挙げられる。塩素原子及び臭素原子、又は塩素イオン及び臭素イオンの合計がそれぞれ上記範囲であることが好ましい。
　ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
　本発明の樹脂組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や本発明の樹脂組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 A conventionally known storage container can be used as the storage container for the resin composition of the present invention. Further, as the storage container, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing contamination of raw materials and the resin composition of the present invention with impurities. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
＜樹脂組成物の硬化物＞
　本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
　本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
　樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が１２０℃～４００℃の範囲内であることがより好ましく、１４０℃～３８０℃の範囲内にあることが更に好ましく、１７０℃～３５０℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物（硬化物からなる膜）の膜厚は、０．５μｍ以上１５０μｍ以下であることが好ましい。
　本発明の樹脂組成物を硬化した際の収縮率は、５０％以下が好ましく、４５％以下がより好ましく、４０％以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
　収縮率［％］＝１００－（硬化後の体積÷硬化前の体積）×１００ <Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape. In the present invention, the cured product is preferably in the form of a film. In addition, by pattern processing of the resin composition, this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100- (volume after curing ÷ volume before curing) x 100
＜樹脂組成物の硬化物の特性＞
　本発明の樹脂組成物の硬化物のイミド化反応率は、７０％以上が好ましく、８０％以上がより好ましく、９０％以上が更に好ましい。７０％未満では硬化物の機械特性が劣る可能性がある。
　本発明の樹脂組成物の硬化物の破断伸びは、３０％以上が好ましく、４０％以上がより好ましく、５０％以上が更に好ましい。
　本発明の樹脂組成物の硬化物のガラス転移温度（Ｔｇ）は、１８０℃以上であることが好ましく、２１０℃以上であることがより好ましく、２３０℃以上であることがさらに好ましい。 <Characteristics of cured product of resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
（現像液）
　本発明の現像液は、本発明の硬化物の製造方法において用いられる現像液である。
　本発明の現像液は、上述の本発明の硬化物の製造方法の現像工程において説明した現像液と同義であり、好ましい態様も同様である。 (Developer)
The developer of the present invention is a developer used in the method for producing a cured product of the present invention.
The developer of the present invention has the same meaning as the developer described in the developing step of the above-mentioned method for producing a cured product of the present invention, and the preferred embodiment is also the same.
　以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「％」は特に述べない限り、質量基準である。 The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
＜アセタール体Ａ－１、Ａ－２の合成＞
Figure JPOXMLDOC01-appb-C000061
 　一口フラスコに、２－フェニルプロピオンアルデヒド（東京化成工業（株）製）３４．９０ｇ（２６０ミリモル）、エチレングリコールモノプロピルエーテル（東京化成工業（株）製）５９．６０ｇ（５７２ミリモル）、（±）－１０－カンファースルホン酸（東京化成工業（株）製）０．６ｇ（２．６ミリモル）、硫酸マグネシウム（東京化成工業（株）製）３０ｇを加えて反応溶液を得た。得られた反応溶液を２５℃で３０分撹拌した後５０℃に昇温し、２４時間撹拌した。攪拌後の溶液を２５℃に冷却し、トリエチルアミン（東京化成工業（株）製）１．３２ｇ（１３ミリモル）を添加した後、酢酸エチル５００ｍＬに溶解し、分液ロートに移した。分液ロート中の酢酸エチル溶液を飽和重曹水２００ｍＬで３回洗浄した後、エバポレーターで溶媒を除去し、アセタール体Ａ－１を７２ｇ得た。 <Synthesis of acetal bodies A-1 and A-2>
Figure JPOXMLDOC01-appb-C000061
 2-Phenylpropionaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 34.90 g (260 mmol), ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 59.60 g (572 mmol), (±) in a bite flask. ) -10-Camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.6 g (2.6 mmol) and magnesium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) 30 g were added to obtain a reaction solution. The obtained reaction solution was stirred at 25 ° C. for 30 minutes, then heated to 50 ° C. and stirred for 24 hours. The stirred solution was cooled to 25 ° C., 1.32 g (13 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, the solution was dissolved in 500 mL of ethyl acetate, and the solution was transferred to a separating funnel. The ethyl acetate solution in the separating funnel was washed 3 times with 200 mL of saturated aqueous sodium hydrogen carbonate, and then the solvent was removed by an evaporator to obtain 72 g of acetal compound A-1.
　同様の方法で、アセタール体Ａ－２を合成した。
Figure JPOXMLDOC01-appb-C000062
 The acetal form A-2 was synthesized in the same manner.
Figure JPOXMLDOC01-appb-C000062
＜クロル体Ｂ－１、Ｂ－２の合成＞
　一口フラスコに上記で合成したＡ－１を７２ｇ、アセチルクロリド（東京化成工業（株）製）１９．１ｇ（２４３ミリモル）を加えて反応溶液を得た。得られた反応溶液を２５℃で１時間攪拌した後４５℃に昇温し、４時間撹拌して、クロル体Ｂ－１を９１ｇ得た。
Figure JPOXMLDOC01-appb-C000063
 <Synthesis of chlor bodies B-1 and B-2>
72 g of A-1 synthesized above and 19.1 g (243 mmol) of acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a bite flask to obtain a reaction solution. The obtained reaction solution was stirred at 25 ° C. for 1 hour, then heated to 45 ° C. and stirred for 4 hours to obtain 91 g of chloroform B-1.
Figure JPOXMLDOC01-appb-C000063
　同様の方法で、クロル体Ｂ－２を合成した。
Figure JPOXMLDOC01-appb-C000064
 Chlor form B-2 was synthesized in the same manner.
Figure JPOXMLDOC01-appb-C000064
＜合成例：ポリマーＰ－１の合成＞
　フラスコに、４，４’－オキシジフタル酸二無水物３１．０２ｇ（１００ミリモル）、Ｎ－メチルピロリドン（ＮＭＰ）１４５ｇを加えた後、２５℃で撹拌しながら、４，４’－ジアミノジフェニルエーテル１８．０２ｇ（９０ミリモル）を添加した。３時間撹拌後、ＮＭＰを１３０ｇ添加し、希釈した。
　得られた希釈液を、－５℃以下に冷却した後、ジイソプロピルエチルアミン２５．８５ｇ（２００ミリモル）を３０分かけて滴下し、次いで２－メトキシエトキシメチルクロリド（東京化成工業（株）製）２４．９１ｇ（２００ミリモル）を１時間かけて滴下し、－１０～－５℃で、１時間撹拌した。得られた攪拌後の溶液をメタノール５Ｌに加えた後、３０分撹拌した。攪拌後の溶液を３０分静置した後、上澄み液を捨て、固形物を得た。この固形物をテトラヒドロフラン３００ｍＬに溶解した後、ヘキサン５Ｌに加え、３０分撹拌し、次いでろ過、乾燥して、ポリマーＰ－１を５６ｇ得た。 <Synthesis example: Synthesis of polymer P-1>
After adding 31.02 g (100 mmol) of 4,4'-oxydiphthalic acid dianhydride and 145 g of N-methylpyrrolidone (NMP) to the flask, while stirring at 25 ° C., 4,4'-diaminodiphenyl ether 18. 02 g (90 mmol) was added. After stirring for 3 hours, 130 g of NMP was added and diluted.
The obtained diluted solution was cooled to -5 ° C or lower, and then 25.85 g (200 mmol) of diisopropylethylamine was added dropwise over 30 minutes, and then 2-methoxyethoxymethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 24. .91 g (200 mmol) was added dropwise over 1 hour and stirred at −10 to −5 ° C. for 1 hour. The obtained stirred solution was added to 5 L of methanol, and the mixture was stirred for 30 minutes. After allowing the stirred solution to stand for 30 minutes, the supernatant was discarded to obtain a solid substance. After dissolving this solid in 300 mL of tetrahydrofuran, it was added to 5 L of hexane, stirred for 30 minutes, then filtered and dried to obtain 56 g of polymer P-1.
＜合成例：ポリマーＰ－２の合成＞
　フラスコに、ｔ－ブチルアルコール９．６４ｇ（１３０ミリモル）、テトラヒドロフラン３０ｍＬを加え、－１０℃に冷却した後、ｎ－ブチルリチウム（２０質量％シクロヘキサン溶液）４３．７ｇを滴下し、ＴＢ－１を得た。
　上記とは別のフラスコ中で、４，４’－オキシジフタル酸二無水物２０．０ｇ（６４．５ミリモル）をジグリム１００ｍＬ中に懸濁させ、ヒドロキノン　０．０５ｇ、ピリジン　１０．７ｇ（１３５ミリモル）を続いて添加し、さらに上記ＴＢ－１を全量滴下ロートを用いて１時間かけて滴下し、その後、２５℃の温度で５時間撹拌した。得られた混合液を－１０℃まで冷却した後、塩化チオニル　１６．１ｇ（１３５．５ミリモル）を９０分かけて滴下して、ピリジニウムヒドロクロリドの白色沈澱物を得た。次いで、白色沈殿物を含む混合液を室温まで温め、２時間撹拌した後、ピリジン　９．７ｇ（１２３ミリモル）及びＮ－メチルピロリドン（ＮＭＰ）　２５ｍＬを添加し、溶液を得た。次いで、得られた溶液に、４，４’－ジアミノジフェニルエーテル　１１．８ｇ（５８．７ミリモル）をＮＭＰ　１００ｍＬ中に溶解させた溶解液を、１時間かけて滴下により添加した。得られた混合液に、メタノール　５．６ｇ（１７．５ミリモル）と３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン　０．０５ｇを加えた後、２時間撹拌した。次いで、攪拌後の混合液を４リットルの水に加えてポリイミド前駆体樹脂を沈殿させた後、５００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体樹脂を濾過して取得した後、４リットルの水に、得られたポリイミド前駆体樹脂を添加し、再度３０分間撹拌し、再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下、４５℃で３日間乾燥し、Ｐ－２を３３ｇ得た。 <Synthesis example: Synthesis of polymer P-2>
To the flask, 9.64 g (130 mmol) of t-butyl alcohol and 30 mL of tetrahydrofuran are added, cooled to −10 ° C., and then 43.7 g of n-butyllithium (20 mass% cyclohexane solution) is added dropwise to add TB-1. Obtained.
In a different flask from the above, 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride was suspended in 100 mL of diglyme, and 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were suspended. Was subsequently added, and the TB-1 was added dropwise over 1 hour using a dropping funnel, and then the mixture was stirred at a temperature of 25 ° C. for 5 hours. After cooling the obtained mixed solution to −10 ° C., 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes to obtain a white precipitate of pyridinium hydrochloride. Then, the mixture containing the white precipitate was warmed to room temperature, stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a solution. Then, to the obtained solution, a solution prepared by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour. To the obtained mixed solution, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, the mixed solution after stirring was added to 4 liters of water to precipitate the polyimide precursor resin, and then the mixture was stirred at a speed of 500 rpm for 15 minutes. After obtaining the polyimide precursor resin by filtration, the obtained polyimide precursor resin was added to 4 liters of water, the mixture was stirred again for 30 minutes, and the mixture was filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain 33 g of P-2.
＜合成例：ポリマーＰ－３の合成＞
　２－メトキシエトキシメチルクロリドの代わりに等モル量のＢ－１を使用した以外は、Ｐ－１と同様の方法でポリマーＰ－３を合成した。 <Synthesis example: Synthesis of polymer P-3>
Polymer P-3 was synthesized in the same manner as P-1 except that an equimolar amount of B-1 was used instead of 2-methoxyethoxymethyl chloride.
＜合成例：ポリマーＰ－４の合成＞
　２－メトキシエトキシメチルクロリドの代わりに等モル量のＢ－２を使用した以外は、Ｐ－１と同様の方法でポリマーＰ－４を合成した。 <Synthesis example: Synthesis of polymer P-4>
Polymer P-4 was synthesized in the same manner as P-1 except that an equimolar amount of B-2 was used instead of 2-methoxyethoxymethyl chloride.
＜合成例：ポリマーＰ－５の合成＞
　フラスコに、４，４’－ビフタル酸無水物２９．４２ｇ（１００ミリモル）、Ｎ－メチルピロリドン（ＮＭＰ）１４５ｇを加えた後、２５℃で撹拌しながら、４，４’－ジアミノジフェニルエーテル１８．０２ｇ（９０ミリモル）を添加した。３時間撹拌後、ＮＭＰを１３０ｇ添加し、希釈した。
　得られた希釈液を、－５℃以下に冷却した後、ジイソプロピルエチルアミン２５．８５ｇ（２００ミリモル）を３０分かけて滴下し、次いでＢ－２（上記合成品）７２．４ｇ（２００ミリモル）を１時間かけて滴下し、－１０～－５℃で、１時間撹拌した。得られた攪拌後の溶液をメタノール５Ｌに加えた後、３０分撹拌した。攪拌後の溶液を３０分静置した後、上澄み液を捨て、固形物を得た。この固形物をテトラヒドロフラン３００ｍＬに溶解した後、ヘキサン５Ｌに加え、３０分撹拌し、次いでろ過、乾燥して、ポリマーＰ－５を５２ｇ得た。 <Synthesis example: Synthesis of polymer P-5>
To a flask, 29.42 g (100 mmol) of 4,4'-biphthalic anhydride and 145 g of N-methylpyrrolidone (NMP) are added, and then 18.02 g of 4,4'-diaminodiphenyl ether is stirred at 25 ° C. (90 mmol) was added. After stirring for 3 hours, 130 g of NMP was added and diluted.
After cooling the obtained diluted solution to -5 ° C. or lower, 25.85 g (200 mmol) of diisopropylethylamine was added dropwise over 30 minutes, and then 72.4 g (200 mmol) of B-2 (the above synthetic product) was added. The mixture was added dropwise over 1 hour, and the mixture was stirred at −10 to −5 ° C. for 1 hour. The obtained stirred solution was added to 5 L of methanol, and the mixture was stirred for 30 minutes. After allowing the stirred solution to stand for 30 minutes, the supernatant was discarded to obtain a solid substance. This solid was dissolved in 300 mL of tetrahydrofuran, added to 5 L of hexane, stirred for 30 minutes, then filtered and dried to give 52 g of polymer P-5.
＜合成例：ポリマーＰ－６の合成＞
　４，４’－ジアミノジフェニルエーテルの添加量を１６．０ｇ（８０ミリモル）に変更した以外、Ｐ－１と同様の方法でポリマーＰ－６を合成した。 <Synthesis example: Synthesis of polymer P-6>
Polymer P-6 was synthesized in the same manner as P-1 except that the amount of 4,4'-diaminodiphenyl ether added was changed to 16.0 g (80 mmol).
＜実施例及び比較例＞
　各実施例において、それぞれ、下記表に記載の成分を混合し、各樹脂組成物を得た。また、比較例において、下記表に記載の成分を混合し、比較用組成物を得た。
　具体的には、表に記載の成分の含有量は、表の「質量部」の欄に記載の量とした。また、各組成物において、溶剤の含有量は、組成物の固形分濃度が表に記載の値（質量％）となるようにした。
　得られた樹脂組成物及び比較用組成物は、フィルタ孔径が０．８μｍのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
　また、表中、「－」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each resin composition. Further, in the comparative example, the components listed in the table below were mixed to obtain a comparative composition.
Specifically, the content of the component described in the table is the amount described in the "Mass part" column of the table. Further, in each composition, the content of the solvent was adjusted so that the solid content concentration of the composition was the value (mass%) shown in the table.
The obtained resin composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter having a filter pore size of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
　表に記載した各成分の詳細は下記の通りである。 The details of each component listed in the table are as follows.
〔樹脂〕
・Ｐ－１～Ｐ－６：上記で合成したＰ－１～Ｐ－６ 〔resin〕
-P-1 to P-6: P-1 to P-6 synthesized above.
〔架橋剤（重合性化合物）〕
・Ｂ－１～Ｂ－４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000069
 [Crosslinking agent (polymerizable compound)]
B-1 to B-4: Compounds with the following structure
Figure JPOXMLDOC01-appb-C000069
〔光酸発生剤〕
・Ｃ－１～Ｃ－４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000070
 [Photoacid generator]
C-1 to C-4: Compounds with the following structure
Figure JPOXMLDOC01-appb-C000070
〔光重合開始剤〕
・Ｉ－１：Ｉｒｇａｃｕｒｅ　ＯＸＥ－０１（ＢＡＳＦ社製） [Photopolymerization initiator]
-I-1: Irgure OXE-01 (manufactured by BASF)
〔シランカップリング剤〕
・Ｄ－１：３－グリシドキシプロピルメチルジメトキシシラン
・Ｄ－２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000071
 〔Silane coupling agent〕
-D-1: 3-glycidoxypropylmethyldimethoxysilane-D-2: a compound having the following structure
Figure JPOXMLDOC01-appb-C000071
〔マイグレーション抑制剤〕
・Ｅ－１：テトラゾール [Migration inhibitor]
・ E-1: Tetrazole
〔添加剤（酸捕捉剤）〕
・Ｆ－１：トリドデシルアミン
・Ｆ－２：トリフェニルイミダゾール
・Ｆ－３：ＤＢＵ（ジアザビシクロウンデセン） [Additives (acid scavengers)]
・ F-1: Tridodecylamine ・ F-2: Triphenylimidazole ・ F-3: DBU (diazabicycloundecene)
〔溶剤〕
・ＧＢＬ：γ－ブチロラクトン
・ＤＭＳＯ：ジメチルスルホキシド
　表中、「比率」の欄の記載は、溶剤の全質量に対する各溶剤の含有量（質量％）を示している。 〔solvent〕
-GBL: γ-butyrolactone-DMSO: dimethyl sulfoxide In the table, the description in the "ratio" column indicates the content (% by mass) of each solvent with respect to the total mass of the solvent.
（評価）
＜解像性評価＞
　各実施例及び比較例において、それぞれ、シリコン基板上に、樹脂組成物または比較用組成物をスピンコート法により塗布して、塗布膜を形成した。次いで、ホットプレートを用いて、表の「ＰＢ温度（℃）」に記載の温度で３００秒間加熱処理を行い、樹脂組成物層を形成した。樹脂組成物層の厚さは、リンス後の膜厚が表中の「変性後膜厚（μｍ）」の欄に記載の値となるよう、適宜変更した。
　次いで、樹脂組成物層に対し、ブロードバンド露光機（ウシオ電機株式会社製：ＵＸ－１０００ＳＮ－ＥＨ０１）にてｉ線フィルターを用いて、露光を行った。露光量は４００ｍＪ／ｃｍ２とした。フォトマスクとしては、トッパンテストチャート（Ｎｏ．１、ネガタイプ、凸版印刷製）を用いた。
　露光後、ホットプレートを用いて、樹脂組成物層を表中の「ＰＥＢ温度（℃）」の欄に記載の温度で、３００分間加熱した。また、「ＰＥＢ温度（℃）」の欄に「－」と記載されて例においては、加熱を行わなかった。
　上記加熱後、表中の「現像液」の欄に記載の現像液を用いて、２３℃で６０秒間現像を行なってパターンを形成した。
　上記現像後、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）でリンスした。
　現像後に得られたパターンを観察し、下記評価基準に従って評価を行った。評価結果は、表中の「解像性」の欄に記載した。
－評価基準－
Ａ：最小開口径が１０μｍ以下であった。
Ｂ：最小開口径が１０μｍを超え２０μｍ以下であった。
Ｃ：最小開口径が２０μｍを超えた。 (evaluation)
<Resolution evaluation>
In each Example and Comparative Example, a resin composition or a comparative composition was applied onto a silicon substrate by a spin coating method to form a coating film. Then, using a hot plate, heat treatment was performed at the temperature described in "PB temperature (° C.)" in the table for 300 seconds to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after rinsing would be the value described in the column of "Film thickness after modification (μm)" in the table.
Next, the resin composition layer was exposed to a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01) using an i-line filter. The exposure amount was 400 mJ / cm 2 . As the photomask, a Toppan test chart (No. 1, negative type, manufactured by Toppan Printing) was used.
After the exposure, the resin composition layer was heated for 300 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example in which "-" was described in the column of "PEB temperature (° C.)", heating was not performed.
After the above heating, a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table.
After the above development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
The pattern obtained after development was observed and evaluated according to the following evaluation criteria. The evaluation results are described in the "Resolution" column in the table.
-Evaluation criteria-
A: The minimum opening diameter was 10 μm or less.
B: The minimum opening diameter was more than 10 μm and 20 μm or less.
C: The minimum opening diameter exceeds 20 μm.
＜多層積層時の１層目寸法安定性評価＞
〔１層目の形成〕
　各実施例及び比較例において、それぞれ、シリコン基板上に樹脂組成物または比較用組成物をスピンコート法により塗布して、塗布膜を形成した。次いで、ホットプレートを用いて、表の「ＰＢ温度（℃）」に記載の温度で３００秒間加熱処理を行い、樹脂組成物層を形成した。樹脂組成物層の厚さは、変性後の膜厚が表中の「変性後膜厚（μｍ）」の欄に記載の値となるよう、適宜変更した。
　次いで、樹脂組成物層に対し、ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、線幅２０μｍの１：１ラインアンドスペースパターンが形成されたフォトマスクを使用して、露光を行った。露光量は４００ｍＪ／ｃｍ２とした。
　露光後、ホットプレートを用いて、樹脂組成物層を表中の「ＰＥＢ温度（℃）」の欄に記載の温度で、５分間加熱した。また、「ＰＥＢ温度（℃）」の欄に「－」と記載されて例においては、加熱を行わなかった。
　上記加熱後、表中の「現像液」の欄に記載の現像液を用いて、２３℃で６０秒間現像を行ってパターンを形成した。
　上記現像後、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）でリンスした。
　上記パターンに対し、表中の「キュア温度（℃）」に記載の温度、「キュア時間（ｍｉｎ）」に記載の時間で加熱を行い、１層目のパターンを得た。
　「加熱手段」の欄に「Ｎ２オーブン」と記載された例においては、Ｋｏｙｏ製、ＣＬＨ－２１を用いて加熱を行った。
　また、「加熱手段」の欄に「ＩＲオーブン」と記載された例においては、アドバンス理工製、ＲＴＰ－６を用いて加熱を行った。 <Evaluation of dimensional stability of the first layer when laminating multiple layers>
[Formation of the first layer]
In each Example and Comparative Example, a resin composition or a comparative composition was applied onto a silicon substrate by a spin coating method to form a coating film. Then, using a hot plate, heat treatment was performed at the temperature described in "PB temperature (° C.)" in the table for 300 seconds to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after modification was the value described in the column of "film thickness after modification (μm)" in the table.
Next, the resin composition layer was exposed to a stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) using a photomask in which a 1: 1 line-and-space pattern having a line width of 20 μm was formed. Was done. The exposure amount was 400 mJ / cm 2 .
After the exposure, the resin composition layer was heated for 5 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example in which "-" was described in the column of "PEB temperature (° C.)", heating was not performed.
After the above heating, a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table.
After the above development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
The above pattern was heated at the temperature described in "cure temperature (° C.)" and the time described in "cure time (min)" in the table to obtain a pattern of the first layer.
In the example described as "N 2 oven" in the "heating means" column, heating was performed using CLH-21 manufactured by Koyo.
Further, in the example described as "IR oven" in the column of "heating means", heating was performed using RTP-6 manufactured by Advanced Riko.
〔２層目の形成〕
　各実施例及び比較例において、それぞれ、上記１層目の硬化物上に、再度、同一の樹脂組成物または比較用組成物をスピンコート法により塗布して、塗布膜を形成した。次いで、ホットプレートを用いて、表の「ＰＢ温度（℃）」に記載の温度で３００秒間加熱処理を行い、樹脂組成物層を形成した。樹脂組成物層の厚さは、変性後の膜厚が表中の「変性後膜厚（μｍ）」の欄に記載の値となるよう、適宜変更した。
　次いで、樹脂組成物層に対し、ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、線幅２０μｍの１：１ラインアンドスペースパターンが形成されたフォトマスクを使用して、露光を行った。上記１：１ラインアンドスペースパターンを介した露光部は、１層目における露光部に対してライン部及びスペース部がそれぞれ直交するように設定した。露光量は４００ｍＪ／ｃｍ２とした。
　露光後、ホットプレートを用いて、樹脂組成物層を表中の「ＰＥＢ温度（℃）」の欄に記載の温度で、５分間加熱した。また、「ＰＥＢ温度（℃）」の欄に「－」と記載された例においては、加熱を行わなかった。
　上記加熱後、表中の「現像液」の欄に記載の現像液を用いて、２３℃で６０秒間現像を行ってパターンを形成した。
　上記現像後、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）でリンスした。
　上記パターンに対し、表中の「キュア温度（℃）」に記載の温度、「キュア時間（ｍｉｎ）」に記載の時間で加熱を行った。
　「加熱手段」の欄に「Ｎ２オーブン」と記載された例においては、Ｋｏｙｏ製、ＣＬＨ－２１を用いて加熱を行い、２層目の硬化物を得た。
　また、「加熱手段」の欄に「ＩＲオーブン」と記載された例においては、アドバンス理工製、ＲＴＰ－６を用いて加熱を行い、２層目の硬化物を得た。 [Formation of the second layer]
In each of the Examples and Comparative Examples, the same resin composition or comparative composition was again applied onto the cured product of the first layer by the spin coating method to form a coating film. Then, using a hot plate, heat treatment was performed at the temperature described in "PB temperature (° C.)" in the table for 300 seconds to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after modification was the value described in the column of "film thickness after modification (μm)" in the table.
Next, the resin composition layer was exposed to a stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) using a photomask in which a 1: 1 line-and-space pattern having a line width of 20 μm was formed. Was done. The exposed portion via the 1: 1 line and space pattern is set so that the line portion and the space portion are orthogonal to the exposed portion in the first layer. The exposure amount was 400 mJ / cm 2 .
After the exposure, the resin composition layer was heated for 5 minutes at the temperature described in the column of "PEB temperature (° C.)" in the table using a hot plate. Further, in the example described as "-" in the column of "PEB temperature (° C.)", heating was not performed.
After the above heating, a pattern was formed by developing at 23 ° C. for 60 seconds using the developer described in the “Developer” column in the table.
After the above development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
The above pattern was heated at the temperature described in "cure temperature (° C.)" and the time described in "cure time (min)" in the table.
In the example described as "N 2 oven" in the column of "heating means", heating was performed using CLH-21 manufactured by Koyo to obtain a cured product of the second layer.
Further, in the example described as "IR oven" in the column of "heating means", heating was performed using RTP-6 manufactured by Advanced Riko Co., Ltd. to obtain a cured product of the second layer.
〔評価〕
　上記１層目の硬化物の形成直後（２層目の形成における塗布膜の形成前）の１層目の硬化物の線幅（線幅Ａ）、及び、上記２層目の硬化物の形成後直後の１層目の硬化物の線幅（線幅Ｂ）を測定し、下記式に従って寸法変動（％）を算出した。上記寸法変動の値から、１層目の寸法安定性を下記評価基準に従って評価した。評価結果は「多層積層時の１層目寸法安定性評価」の欄に記載した。
　寸法変動（％）＝｜線幅Ａ－線幅Ｂ｜／線幅Ａ×１００－評価基準－
　Ａ：寸法変動（％）が５％以下であった。
　Ｂ：寸法変動（％）が５％を超えた。 〔evaluation〕
Immediately after the formation of the cured product of the first layer (before the formation of the coating film in the formation of the second layer), the line width (line width A) of the cured product of the first layer and the formation of the cured product of the second layer. The line width (line width B) of the cured product of the first layer immediately after that was measured, and the dimensional variation (%) was calculated according to the following formula. From the above dimensional variation values, the dimensional stability of the first layer was evaluated according to the following evaluation criteria. The evaluation results are described in the column of "Evaluation of dimensional stability of the first layer at the time of multi-layer stacking".
Dimensional variation (%) = | Line width A-Line width B | / Line width A x 100-Evaluation criteria-
A: The dimensional variation (%) was 5% or less.
B: Dimensional variation (%) exceeded 5%.
＜多層積層時の２層目解像性評価＞
　上記多層積層時の１層目寸法安定性評価と同様の方法により、１層目の硬化物及び２層目の硬化物を作製した。
　２層目の硬化物を観察し、下記評価基準に従って評価を行った。評価結果は、表中の「多層積層時の２層目解像性評価」の欄に記載した。
－評価基準－
　Ａ：基材表面とパターンの側面のなす角であるテーパ角が８０°以上９０°未満であり、パターンの剥がれが認められなかった。
　Ｂ：テーパ角が８０°未満であるか、パターンの断面形状が９０°を超えるテーパ角をなす逆テーパ形状であるか、又は、パターンの断面形状がくびれた形状であるが、パターンの剥がれは認められなかった。
　Ｃ：パターンの剥がれが認められた。 <Evaluation of second layer resolution when stacking multiple layers>
A cured product of the first layer and a cured product of the second layer were produced by the same method as in the evaluation of the dimensional stability of the first layer at the time of laminating the multiple layers.
The cured product of the second layer was observed and evaluated according to the following evaluation criteria. The evaluation results are described in the column of "evaluation of second layer resolution at the time of multi-layer stacking" in the table.
-Evaluation criteria-
A: The taper angle formed by the surface of the base material and the side surface of the pattern was 80 ° or more and less than 90 °, and no peeling of the pattern was observed.
B: The taper angle is less than 80 °, the cross-sectional shape of the pattern is a reverse taper shape with a taper angle of more than 90 °, or the cross-sectional shape of the pattern is constricted, but the pattern is peeled off. I was not able to admit.
C: Peeling of the pattern was observed.
　比較例１に係る硬化物の製造方法は、ポリイミド前駆体が酸の作用により極性が増大する反応を生じる基を有せず、いわゆるネガ型のパターン形成が行われている。このような例においては、解像性に劣ることがわかる。 In the method for producing a cured product according to Comparative Example 1, the polyimide precursor does not have a group that causes a reaction in which the polarity is increased by the action of an acid, and so-called negative pattern formation is performed. In such an example, it can be seen that the resolution is inferior.
＜実施例１０１＞
　実施例１において使用した樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、１００℃で３００秒間乾燥した。膜厚は得られる硬化物の膜厚が５μｍとなる膜厚とした。その後、ステッパー（（株）ニコン製、ＮＳＲ１５０５　ｉ６）を用いて露光した。露光はマスク（パターンが１：１ラインアンドスペースであり、線幅が１０μｍであるバイナリマスク）を介して、波長３６５ｎｍで行った。露光後、１２０℃で３００秒間加熱した。上記加熱後、実施例１で用いた現像液で現像し、実施例１で用いたリンス液でリンスして、層のパターンを得た。
　次いで、窒素雰囲気下で、１０℃／分の昇温速度で昇温し、２３０℃に達した後、１２０分間維持して層を硬化し、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
　また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <Example 101>
The resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 300 seconds. The film thickness was set so that the film thickness of the obtained cured product was 5 μm. Then, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 120 ° C. for 300 seconds. After the above heating, it was developed with the developer used in Example 1 and rinsed with the rinse solution used in Example 1 to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the layer was cured by maintaining for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (14)

  1. 　樹脂、活性光線又は放射線の照射により酸を発生する化合物、及び、溶剤を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、
    　前記膜を選択的に露光する露光工程、
    　前記露光後の膜を現像液を用いて現像してパターンを形成する現像工程、並びに、
    　前記パターンを変性させる変性工程を含み、
    　前記樹脂がポリイミド前駆体であり、
    　前記樹脂は酸の作用により極性が増大する反応を生じる基を有し、
    　前記現像液の全質量に対する有機溶剤の含有量が８０質量％以上であり、
    　前記変性により、前記樹脂組成物が含む溶剤に対して前記パターンの溶解性が低下する、
    　硬化物の製造方法。     A film forming step of applying a resin, a compound that generates an acid by irradiation with active light or radiation, and a resin composition containing a solvent onto a substrate to form a film.
    An exposure process that selectively exposes the film,
    A developing step of developing the exposed film with a developing solution to form a pattern, and
    Including a modification step of modifying the pattern.
    The resin is a polyimide precursor,
    The resin has a group that causes a reaction in which the polarity is increased by the action of an acid.
    The content of the organic solvent with respect to the total mass of the developer is 80% by mass or more, and the content is 80% by mass or more.
    The modification reduces the solubility of the pattern in the solvent contained in the resin composition.
    A method for manufacturing a cured product.
  2. 　得られる硬化物の膜厚が５μｍ以上である、請求項１に記載の硬化物の製造方法。 The method for producing a cured product according to claim 1, wherein the obtained cured product has a film thickness of 5 μm or more.
  3. 　前記樹脂が下記式（１）で表される繰返し単位を含む、請求項１又は２に記載の硬化物の製造方法。
    Figure JPOXMLDOC01-appb-C000001
     　上記式（１）中、Ｒ１は、４価の有機基を表す；複数のＲ１は互いに同一であっても異なっていてもよい；Ｒ２は、２価の有機基を表す；複数のＲ２は互いに同一であっても異なっていてもよい；Ｒ３は、各々独立に、水素原子又は有機基を表す。     The method for producing a cured product according to claim 1 or 2, wherein the resin contains a repeating unit represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     In formula (1) above, R 1 represents a tetravalent organic group; a plurality of R 1s may be the same or different from each other; R 2 represents a divalent organic group; R 2 may be the same as or different from each other; R 3 each independently represents a hydrogen atom or an organic group.
  4. 　前記式（１）で表される繰り返し単位が前記酸の作用により極性が増大する反応を生じる基を有する、請求項３に記載の硬化物の製造方法。 The method for producing a cured product according to claim 3, wherein the repeating unit represented by the formula (1) has a group that causes a reaction in which the polarity is increased by the action of the acid.
  5. 　前記樹脂組成物が酸捕捉剤を更に含む、請求項１～４のいずれか１項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 4, wherein the resin composition further contains an acid scavenger.
  6. 　前記現像液が、ハンセン溶解度パラメータの水素結合項ｄＨの値が８以下である有機溶剤を８０質量％以上含む、請求項１～５のいずれか１項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 5, wherein the developer contains 80% by mass or more of an organic solvent having a value of the hydrogen bond item dH of the Hansen solubility parameter of 8 or less.
  7. 　前記酸の作用により極性が増大する反応を生じる基が下記式（Ａ－１）又は下記式（Ａ－２）で表される基である、請求項１～６のいずれか１項に記載の硬化物の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     　式（Ａ－１）中、ＲＡ１～ＲＡ５はそれぞれ独立に、水素原子又は１価の有機基を表し、ＲＡ１～ＲＡ５のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す；
    　式（Ａ－２）中、ＲＡ６～ＲＡ８はそれぞれ独立に、１価の有機基を表し、ＲＡ６～ＲＡ８のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結
    合部位を表す。     The group according to any one of claims 1 to 6, wherein the group that causes a reaction in which the polarity is increased by the action of the acid is a group represented by the following formula (A-1) or the following formula (A-2). How to make a cured product.
    Figure JPOXMLDOC01-appb-C000002
     In the formula (A-1), RA1 to RA5 each independently represent a hydrogen atom or a monovalent organic group, and even if at least two of RA1 to RA5 are bonded to form a ring structure. Often, * represents the binding site with other structures;
    In the formula (A-2), RA6 to RA8 each independently represent a monovalent organic group, and at least two of RA6 to RA8 may be bonded to form a ring structure *. Represents a binding site with another structure.
  8. 　前記変性工程において、前記パターンの加熱が行われる、請求項１～７のいずれか１項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 7, wherein the pattern is heated in the modification step.
  9. 　前記露光工程後、前記現像工程前に、前記膜を加熱する工程を更に含む、請求項１～８のいずれか１項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 8, further comprising a step of heating the film after the exposure step and before the development step.
  10. 　請求項１～９のいずれか１項に記載の硬化物の製造方法を複数回繰り返すことを含む　積層体の製造方法。 A method for producing a laminated body, which comprises repeating the method for producing a cured product according to any one of claims 1 to 9 multiple times.
  11. 　複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含む、請求項１０に記載の積層体の製造方法。 The method for producing a laminate according to claim 10, further comprising a metal layer forming step of forming a metal layer on a layer made of the cured product during a method for producing a cured product which is performed a plurality of times.
  12. 　請求項１～９のいずれか１項に記載の硬化物の製造方法、又は、請求項１０若しくは１１に記載の積層体の製造方法を工程として含む、
    　電子デバイスの製造方法。     The method for producing a cured product according to any one of claims 1 to 9 or the method for producing a laminate according to claim 10 or 11 is included as a step.
    How to manufacture electronic devices.
  13. 　請求項１～９のいずれか１項に記載の硬化物の製造方法に用いられる樹脂組成物。 A resin composition used in the method for producing a cured product according to any one of claims 1 to 9.
  14. 　請求項１～９のいずれか１項に記載の硬化物の製造方法に用いられる現像液。 A developer used in the method for producing a cured product according to any one of claims 1 to 9.
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JP2009244479A (en) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd Photosensitive resin composition, article and pattern forming method
WO2013141376A1 (en) * 2012-03-23 2013-09-26 富士フイルム株式会社 Protectant, method for producing compound protected by protectant, resin protected by protectant, photosensitive resin composition containing resin protected by protectant, pattern-forming material, photosensitive film, cured relief pattern, method for producing same, and semiconductor device
WO2018199247A1 (en) * 2017-04-26 2018-11-01 日立化成株式会社 Photosensitive resin composition and method for forming resist pattern

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JP5724515B2 (en) 2010-03-31 2015-05-27 大日本印刷株式会社 Relief pattern manufacturing method and electronic component
TWI767436B (en) * 2016-02-26 2022-06-11 日商富士軟片股份有限公司 Manufacturing method of laminated body, manufacturing method of semiconductor element, and manufacturing method of rewiring layer
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JP2009244479A (en) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd Photosensitive resin composition, article and pattern forming method
WO2013141376A1 (en) * 2012-03-23 2013-09-26 富士フイルム株式会社 Protectant, method for producing compound protected by protectant, resin protected by protectant, photosensitive resin composition containing resin protected by protectant, pattern-forming material, photosensitive film, cured relief pattern, method for producing same, and semiconductor device
WO2018199247A1 (en) * 2017-04-26 2018-11-01 日立化成株式会社 Photosensitive resin composition and method for forming resist pattern

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