KR20230019921A - A method for producing a cured product, a resin composition, a developing solution, a method for producing a laminate, and a method for producing a semiconductor device - Google Patents

Abstract

The present invention provides a method for producing a cured product having excellent resolution, a resin composition and a developing solution used in the method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing the cured product or the laminate. A manufacturing method of an electronic device including a manufacturing method of a sieve is provided. The method for producing a cured product includes a film formation step using a resin composition containing a compound that generates an acid by exposure and a solvent, an exposure step, a developing step, and a denaturation step, wherein the resin is a polyimide precursor, The resin has a group that generates a reaction in which polarity is increased by the action of an acid, the content of the organic solvent in the developing solution is 80% by mass or more, and the solubility of the pattern with respect to the solvent contained in the resin composition is reduced by modification. It is lowered.

Description

A method for producing a cured product, a resin composition, a developing solution, a method for producing a laminate, and a method for producing a semiconductor device

The present invention relates to a method for producing a cured product, a resin composition, a developing solution, a method for producing a laminate, and a method for manufacturing a semiconductor device.

Since resins such as polyimide are excellent in heat resistance, insulating properties, etc., they are applied to various applications. The use is not particularly limited, but when a semiconductor device for mounting is taken as an example, a pattern made of these resins may be used as a material for an insulating film or sealing material, or as a protective film. In addition, patterns made of these resins are also used as base films and cover lays for flexible substrates.

For example, in the applications described above, 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 thereafter performing exposure, development, modification, etc. as necessary. can

Since the resin composition can be applied by a known coating method or the like and can form a fine pattern, a complex pattern or the like by development, it can be said that the cured film has a high degree of freedom in design and is excellent in manufacturing adaptability. . In addition to the high performance of polyimide and the like, from the viewpoint of excellent adaptability in manufacturing, industrial application development of a method for producing a cured product using a resin composition containing a polyimide precursor is increasingly expected.

For example, in Patent Document 1, a phenomenon in which a coating film or molded body is formed using a negative photosensitive resin composition, and after irradiating electromagnetic waves to the coated film or molded body in a predetermined pattern, the coating film of unexposed areas is removed to form a pattern. A method for manufacturing a relief pattern having a step of heating the coating film or molded body before the step, wherein in the heating step, gas is actively and continuously supplied from outside the system, and volatile components generated from the coating film or molded body are A method for producing a relief pattern is described, characterized in that it is a step of heating the coating film or molded body through a heat medium or by electromagnetic wave radiation in an atmosphere that is actively removed from the system.

Patent Document 1: Japanese Unexamined Patent Publication No. 2011-227485

In conventional methods for producing cured products, it is desired to improve resolution.

The present invention provides a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developer used in the method for producing the cured product, and a method for producing a laminate including the method for producing the cured product, and It is an object of the present invention to provide a method of manufacturing an electronic device including the method of manufacturing the cured product or the method of manufacturing the laminate.

Examples of representative embodiments of the present invention are shown below.

<1> A film forming step of forming a film by applying a resin composition containing a resin, a compound that generates an acid by irradiation with actinic rays or radiation, and a solvent on a substrate;

An exposure step of selectively exposing the film to light;

A developing step of developing the film after exposure using a developer to form a pattern, and

A denaturation step of denaturing the pattern;

The resin is a polyimide precursor,

The resin has a group that generates a reaction in which polarity is increased by the action of an acid,

The content of the organic solvent relative to the total mass of the developer is 80% by mass or more,

The method for producing a cured product in which the solubility of the pattern in the solvent contained in the resin composition is reduced by the modification.

<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 formula (1) below.

[Formula 1]

In the formula (1), R ¹ represents a tetravalent organic group; A plurality of R ¹ may be the same as or different from each other; R ² represents a divalent organic group; A plurality of 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 Formula (1) has a group generating a reaction in which polarity is increased by the action of the acid.

<5> The method for producing a cured product according to any one of <1> to <4>, in which the resin composition further contains an acid trapping agent.

<6> The method for producing a 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 hydrogen bond term dH value of 8 or less in the Hansen solubility parameter.

<7> Curing according to any one of <1> to <6>, wherein the group generating 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 water.

[Formula 2]

In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * indicates another structure indicates a binding site with;

In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, and at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * is a bond with another structure. indicates the area.

<8> The method for producing a cured product according to any one of <1> to <7>, wherein in the modification step, the pattern is heated.

<9> The method for producing a cured product according to any one of <1> to <8>, further including a step of heating the film after the exposure step and before the image development step.

<10> A method for producing a laminate comprising 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>, which further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the methods for producing a cured product performed a plurality of times.

<12> The manufacturing method of an electronic device including the manufacturing method of the hardened|cured material in any one of <1>-<9>, or the manufacturing method of a laminated body as described in <10> or <11>.

<13> The resin composition used for the manufacturing method of the hardened|cured material in any one of <1>-<9>.

<14> A developing solution used in the method for producing a cured product according to any one of <1> to <9>.

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 developer used in the method for producing the cured product, and a method for producing a laminate including the method for producing the cured product, and , A method of manufacturing an electronic device including the method of manufacturing the cured product or the method of manufacturing the laminate is provided.

EMBODIMENT OF THE INVENTION Hereinafter, the main embodiment of this invention is described. However, the present invention is not limited to the specific embodiments.

In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively.

In this specification, the word "process" is meant to include 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 this specification, the notation that does not describe substitution and unsubstitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. 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).

In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of light used for exposure include bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams, or radiation.

In the present specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acryl" refers to "acryl" and "methacryl". “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

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.

In this specification, the total solid content refers to the total mass of components excluding the solvent from all components of the composition. In addition, in this specification, solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values, unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220GPC (manufactured by Tosoh Co., Ltd.), and as a column, guard column HZ-L, TSKgel Super HZM- M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (above, manufactured by Tosoh Co., Ltd.) are connected in series and used. These molecular weights shall be measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, detection in the GPC measurement assumes that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the reference layer among a plurality of layers of interest It is only necessary if there is another layer on the upper or lower side. That is, a third layer or element may be further interposed between the layer serving as the standard and the other layer, and the layer serving as the standard and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which layers are laminated with respect to the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", The opposite direction is referred to as "lower". Note that the setting of such a vertical direction is for convenience in this specification, and in an actual aspect, there may be cases where the “upper” direction in this specification is different from vertically upward.

In this specification, as long as there is no special description, a composition may also contain two or more types of compounds corresponding to the component as each component contained in a composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.

In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

In this specification, a combination of preferable aspects is a more preferable aspect.

(Method of producing cured product)

In the method for producing a cured product of the present invention, a resin composition containing a resin, a compound that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "photoacid generator"), and a solvent is applied to a substrate. A film forming process of forming a film by using actinic light or radiation, an exposure process of pattern exposure of the film using actinic light or radiation, a developing process of developing a film after exposure with a developer to obtain a pattern, and a denaturation process of modifying the pattern. And, the resin is a polyimide precursor, the resin has a group that generates a reaction in which polarity is increased by the action of an acid (hereinafter, also referred to as a "polarity converter"), and an organic solvent based on the total mass of the developing solution It is a method for producing a cured product in which the content of is 80% by mass or more, and the solubility of the pattern in the solvent contained in the resin composition decreases due to the modification.

Hereinafter, in this invention, resin which is a polyimide precursor and has a polarity converter is also called "specific resin."

According to the method for producing a cured product of the present invention, a cured product having excellent resolution is obtained.

Although the mechanism by which the said effect is obtained is unknown, it is guessed as follows.

A negative pattern can be formed by using a film formed from a resin composition containing a polyimide precursor having a polarity converter and a photoacid generator, and using a developing solution having an organic solvent content of 80% by mass or more.

The negative pattern refers to a pattern in which the unexposed portion of the film is removed in the developing step.

Specifically, in the exposure step, acid is generated from a photoacid generator in the exposed portion, and the action of the acid increases the polarity of the resin in the polarity converter. Solubility is reduced, and after the development process, the exposed portion remains and the unexposed portion is removed.

Here, since penetration of the developing solution into the exposed portion is suppressed by the increase in the polarity, it is considered that the swelling of the obtained pattern due to the developing solution is suppressed.

It is thought that suppression of the swelling makes it easy to obtain an open hole pattern even in a fine hole pattern, for example, when a hole pattern is formed.

In addition, it is thought that suppression of the swelling suppresses swelling of the line portion in the case of forming a line pattern, for example, so that a finer line pattern can be easily formed.

That is, according to the method for producing a cured product of the present invention, a fine pattern can be formed, and it can be said that the resolution is excellent.

In addition, since the solubility of the composition of the present invention in the solvent contained in the resin composition decreases due to modification, even when another resin composition is applied to the obtained pattern to form a laminated structure, the pattern does not dissolve in the resin composition. It is difficult, and the dimensional stability of the first-layer pattern at the time of lamination is excellent, and the resolution of the second-layer pattern at the time of lamination is excellent.

Here, Patent Literature 1 uses a film formed of a resin composition containing a polyimide precursor having a polarity converter and a photoacid generator, and uses a developing solution having an organic solvent content of 80% by mass or more. It is not described. .

Hereinafter, the method for producing the cured product of the present invention will be described in detail.

<Film formation process>

The method for producing a cured product of the present invention includes a film forming step of forming a film by applying a resin composition containing a resin, a compound that generates an acid by irradiation with actinic rays or radiation, and a solvent on a substrate.

The detail of the resin composition used in this invention is mentioned later.

〔write〕

The type of base material can be appropriately determined depending on the application, but semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, Ni , metal substrates such as Cu, Cr, and Fe (for example, a substrate formed of metal and a substrate in which a metal layer is formed, for example, by plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates of plasma display panels (PDP), and the like, are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

In addition, the shape of the substrate is not particularly limited, and may be circular or rectangular.

As the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm.

Moreover, as a base material, for example, a plate shape, preferably a panel shape base material (substrate) is used.

In the case of forming a film by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured material) or the surface of a metal layer, the resin layer or metal layer serves as the base material.

As a means for applying the resin composition of the present invention onto a substrate, application is preferable.

As the means to be applied, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, ink jet law, etc. From the viewpoint of uniformity of film thickness, more preferably a spin coating method, a slit coating method, a spray coating method, or an inkjet method. From the viewpoint of uniformity of film thickness and productivity, the spin coating method and the slit coating method are preferred. do. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferable, and for rectangular substrates, slit coating, spray coating, and inkjet methods are preferred. etc. are preferred. In the case of the spin coating method, it can be applied for about 10 seconds to 3 minutes at a rotational speed of 500 to 3,500 rpm, for example.

Moreover, a method of transferring onto a base material a coating film applied and formed on a temporary support body in advance by the above application method can also be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

Moreover, you may perform the process of removing an excess film|membrane in the edge part of a base material. Examples of such a process include edge bead rinse (EBR), back rinse, and the like.

Alternatively, a pre-wet process may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

<Drying process>

After the film formation process (layer formation process), the film may be subjected to a process of drying the formed film (layer) in order to remove the solvent (drying process).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step.

Moreover, it is preferable that the said drying process is performed after a film formation process and before an exposure process.

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. Moreover, you may dry by reduced pressure. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 2 minutes - 7 minutes are more preferable.

<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 in the film formation step.

Exposing selectively means exposing a part of the film. Further, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed in the film.

The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, for example. more preferable

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

Regarding the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) , F ₂ excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

In addition, the method of exposure is not particularly limited, and any method is sufficient as long as 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, and the like are exemplified.

<Post-exposure heating process>

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 in the exposure step.

The post-exposure heating step can be performed after the exposure step and before the developing step.

It is preferable that it is 50 degreeC - 140 degreeC, and, as for the heating temperature in the heating process after exposure, it is more preferable that it is 60 degreeC - 120 degreeC.

30 seconds - 300 minutes are preferable, and, as for the heating time in a heating process after exposure, 1 minute - 10 minutes are more preferable.

The temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/minute, more preferably 2 to 10°C/minute, and still more preferably 3 to 10°C/minute from the temperature at the start of heating to the maximum heating temperature.

Moreover, you may change the temperature increase rate suitably in the middle of heating.

Moreover, the aspect which heats by the hot plate or oven etc. which have been set to the desired temperature is also preferable.

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.

Moreover, it is also preferable to carry out in the atmosphere of low oxygen concentration by flowing an inert gas, such as nitrogen, helium, and argon, at the time of heating.

<Development process>

The film after exposure is subjected to a developing process in which a pattern is formed by developing using a developing solution.

That is, the method for producing a cured product of the present invention includes a developing step of forming a pattern by developing a film exposed by the exposure step using a developing solution.

By performing development, the unexposed portion of the film is removed and a pattern is formed.

Here, a phenomenon in which an unexposed portion of a film is removed by a developing process is referred to as a negative-type phenomenon, and a phenomenon in which an exposed portion of a film is removed by a developing process is referred to as a positive-type phenomenon.

〔developer〕

The content of the organic solvent with respect to the total mass of the developing solution used in the manufacturing method of the cured film of this invention is 80 mass % or more.

-Organic Solvent-

The developing solution preferably contains 90% by mass or more of the organic solvent, more preferably 95% by mass or more, and even more preferably 98% by mass or more of the organic solvent with respect to 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.

In addition, the developer preferably contains 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more of an organic solvent having a value of 8 or less in the hydrogen bond term dH of the Hansen solubility parameter. It is preferable, and it is especially preferable to include 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 organic solvents is a value calculated using Hansen Solubility Parameter Software (HSPiP).

The organic solvent is esters, 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, alkyloxyacetic acid (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxyacetic acid) methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg: 3-alkyloxymethylpropionate, 3-alkyloxyethylpropionate, etc.) (e.g., 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., 2-alkyl Methyl oxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g., 2-methoxy-2-methylmethylpropionate, ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Col 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 monopropyl ether acetate, and the like, and as ketones, for example, ethyl 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, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol as alcohols, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be suitably

When the developing solution contains an organic solvent, the organic solvent can be used alone or in combination of two or more. 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 preferred. A developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferable, and a developing solution containing cyclopentanone is most preferable.

The developing solution may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[Supply Method of Developer]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed. A method of immersing a film-formed substrate in a developer, a puddle phenomenon in which a developer is supplied to a film formed on a substrate using a nozzle, or a developer is continuously applied. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

From the viewpoints of penetrability of the developer, removability of the non-image portion, and manufacturing efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferable, and from the viewpoint of penetrability of the developer into the image portion, the spray The method of supplying with a nozzle is more preferable.

Alternatively, after continuously supplying the developing solution with a straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, a step of continuously supplying the developing solution with the straight nozzle again and then spinning the base material to remove the developing solution from the base material may be employed. , You may repeat this process multiple times.

Further, as a method for supplying the developing solution in the developing step, a step in which the developing solution is continuously supplied to the substrate, a step in which the developing solution is maintained on the substrate in a substantially stationary state, a step in which the developing solution is vibrated on the substrate with ultrasonic waves or the like, and a process in which they are combined. etc. can be employed.

As development time, 10 second - 10 minutes are preferable and 20 second - 5 minutes are more preferable. 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.

In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with a rinsing solution. Moreover, you may employ|adopt the method of supplying a rinsing liquid while the developing solution which touches on a pattern is not completely dry.

[rinse liquid]

When the developing solution is an aqueous alkali solution, water can be used as a rinse solution, for example. When the developing solution is a developing solution containing an organic solvent, for example, a solvent different from the solvent contained in the developing solution (eg, water, an organic solvent different from the organic solvent contained in the developing solution) can be used as the rinsing solution. there is.

Examples of the organic solvent in case the rinse liquid contains an organic solvent include esters such as 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, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxy butyl acetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g. 3-alkyloxy Methyl propionate, 3-alkyloxyethylpropionate, etc. (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxy Alkyl esters of propionic acid (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropionate, Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy -2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate 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 Lycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic carbonized water Examples of the element include aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, and alcohols as alcohols. isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N- Ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, and cyclopentanone, γ-butyrolactone, dimethylsulfoxide Side, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are still more preferable.

When the rinsing liquid contains an organic solvent, the rinsing liquid preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and more preferably 90% by mass or more of an organic solvent do. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

The rinse liquid may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply rinse liquid]

The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and a method of immersing the substrate in the rinsing liquid, a puddle phenomenon on the substrate, a method of supplying the rinsing liquid to the substrate with a shower, and a straight nozzle on the substrate There is a method of continuously supplying a developing solution by such means.

From the viewpoint of permeability of the rinse liquid, removability of the non-image area, and manufacturing efficiency, there is a method of supplying the rinse liquid to a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid to the spray nozzle is preferable, and the image area From the viewpoint of permeability of the rinsing liquid to the water, a method of supplying through a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

That is, the rinsing step is preferably a step of supplying a rinsing liquid to the film after exposure through a straight nozzle or continuously supplying the rinsing liquid to the film after exposure, and more preferably a process of supplying the rinsing liquid through a spray nozzle.

Further, as a method for supplying the rinsing liquid in the rinsing step, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is maintained on the substrate in a substantially stationary state, a process in which the rinsing liquid is vibrated on the substrate with ultrasonic waves, and A process or the like combining them is employable.

As rinse time, 10 seconds - 10 minutes are preferable, and 20 seconds - 5 minutes are more preferable. 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.

<denaturation process>

The method for producing a cured product of the present invention includes a modification step of modifying the pattern (pattern obtained by the developing step).

It is preferable that a modification|denaturation process is a process of imidating the said polyimide precursor within the said pattern.

Further, in the denaturation step, it is preferable that the pattern is heated.

That is, it is preferable that a modification|denaturation process is a process of performing imidation of the said polyimide precursor within the said pattern by heating.

It is preferable to perform heating by the method described in the following heating process.

<Heating process>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a heating step of heating the pattern obtained by the above development.

That is, the manufacturing method of the hardened|cured material of this invention may also include the heating process of heating the pattern obtained by the image development process.

Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method or a film obtained by the film forming step without performing the developing step.

In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide.

Further, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds.

The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, still more preferably 150 to 250 ° C, still more preferably 160 to 250 ° C, 160 ° C ~230°C is particularly preferred.

The heating in the heating step is preferably performed at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10°C/minute, more preferably 3 to 10°C/minute. By setting the temperature increase rate to 1 ° C./min or more, excessive volatilization of the acid or solvent can be prevented while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, residual stress of the cured product can be relaxed.

Further, in the case of an oven capable of rapid heating, heating is performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec. desirable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the process of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied on a substrate and then dried, the temperature of the film (layer) after this drying is, for example, 30 to higher than the boiling point of the solvent contained in the resin composition of the present invention. It is preferable to raise the temperature from a temperature as low as 200°C.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and still more preferably 15 to 240 minutes.

In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, still more preferably 100°C or higher, and particularly preferably 120°C or higher, from the viewpoint of adhesion between layers. .

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and still more preferably 240°C or lower.

Heating may be performed stepwise. As an example, a process such as raising the temperature from 25 ° C to 120 ° C at 3 ° C / min, holding at 120 ° C for 60 minutes, raising the temperature from 120 ° C to 180 ° C at 2 ° C / min and holding at 180 ° C for 120 minutes You can do it. Moreover, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in a short time of about 10 second - about 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be carried out in two or more stages, for example, a first stage pretreatment step may be performed in the range of 100 to 150 ° C., followed by a second stage pretreatment step in the range of 150 to 200 ° C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degrees C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon or under reduced pressure 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.

Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electrothermal oven, a hot air oven, an infrared oven, etc. are mentioned.

<Exposure process after development>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a post-development exposure step of exposing the pattern after the developing step to light in addition to the heating step.

That is, the method for producing a cured product of the present invention may also include a post-development exposure step of 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 the heating step and the post-development exposure step.

In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by photosensitization of a photobase generator, a reaction in which acid-decomposable groups are desorbed by photosensitization of a photoacid generator, etc. are promoted. can make it

In the post-development exposure process, at least a part of the pattern obtained in the development process may be exposed, but it is preferable that all of the patterns are exposed.

The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity.

The post-development exposure process can be performed using, for example, the light source in the exposure process described above, and broadband light is preferably used.

<Metal layer formation process>

The pattern obtained by the developing step (preferably provided in at least one of the heating step and the post-exposure developing step) may be subjected to a metal layer forming step of forming a 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 (preferably applied to a heating step) obtained by the developing step.

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, and copper and Aluminum is more preferred, and copper is more preferred.

The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, Japanese Unexamined Patent Publication No. 2007-157879, Japanese Publication No. 2001-521288, Japanese Unexamined Patent Publication No. 2004-214501, Japanese Unexamined Patent Publication No. 2004-101850, US Patent Publication No. 7888181B2, US Patent Publication No. The method described in 9177926B2 can be used. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified. As a preferable aspect of plating, electrolytic plating using a copper sulfate or copper cyanide plating solution is exemplified.

The thickness of the metal layer is preferably 0.01 μm to 50 μm, and more preferably 1 μm to 10 μm in the thickest part.

<Use>

Examples of the manufacturing method of the cured product of the present invention or applicable fields of the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, pattern formation of a sealing film, a substrate material (a base film or cover lay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting use as described above by etching may be used. Regarding these applications, for example, Science & Technology Co., Ltd. "Highly functional polyimide and application technology" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Basics and development of polyimide materials" November 2011 Monthly publication, Japanese Polyimide/Aromatic Polymer Research Society/edition "Latest Polyimide Basics and Applications" N.T.S., August 2010, etc. can be referenced.

In addition, the production method of the cured product of the present invention or the cured product of the present invention is used for producing a plate surface such as an offset plate surface or a screen plate surface, for use in etching of molded parts, in electronics, in particular, as a protective lacquer in microelectronics, and It can also be used for production of dielectric layers and the like.

Further, the film thickness of the cured product obtained by the method for producing a 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, from the viewpoint of, for example, the insulating property of the cured product, 20 μm or more is particularly preferred. Although the upper limit of the said film thickness is not specifically limited, For example, it can be 50 micrometers or less.

According to the method for producing a cured product of the present invention, a cured product having excellent resolution can be produced even when the film thickness is relatively thick.

(Laminate and manufacturing method of the laminate)

The laminate of the present invention refers to a structure having a plurality of layers comprising a cured product of the present invention.

The laminate of the present invention is a laminate comprising two or more layers of cured material, and may be a laminate of three or more layers.

At least one of the two or more layers of the cured material included in the laminate is a layer made of the cured material of the present invention, and from the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to the shrinkage, It is also preferable that all the layers made of the cured material included in the laminate are layers made of the cured material of the present invention.

That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes repeating the manufacturing method of the cured product of the present invention a plurality of times.

It is preferable that the layered product of the present invention includes two or more layers of layers made of a cured product and includes a metal layer between any one of the layers made of the cured product. It is preferable that the said metal layer is formed by the said metal layer formation process.

That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation process of forming a metal layer on the layer which consists of hardened|cured material between the manufacturing method of hardened|cured material performed multiple times. Preferred aspects of the metal layer forming process are as described above.

As the above-mentioned laminate, a laminate containing at least a layered structure in which three layers, for example, a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order, is mentioned as a preferable one. .

It is preferable that both the layer composed of the first cured material and the layer composed of the second cured material are layers made of the cured material of the present invention. The resin composition of the present invention used for forming the layer composed of the first cured material and the resin composition of the present invention used for forming the layer composed of the second cured material may be compositions having the same composition or different in composition. It may be a composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Laminating process>

It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process.

The lamination step is, on the surface of the pattern (resin layer) or metal layer, (a) film formation step (layer formation step), (b) exposure step, (c) developing step, and (d) heating step in this order. It is a series of steps including performing with However, an aspect in which the film formation step of (a) and the heating step (d) are repeated may be used. Moreover, you may include (e) metal layer formation process after (d) heating process. It goes without saying that the above drying step or the like may be appropriately further included in the lamination step.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the exposure process, the heating process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

It is preferable to perform the said lamination process 2 to 20 times, and it is more preferable to perform it 2 to 9 times.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 2 or more layers and 20 or less layers, and more preferably 2 or more layers and 9 or less layers. .

Each of the above layers may be the same or different in composition, shape, film thickness, and the like.

In this invention, after providing a metal layer especially, the aspect which further forms the hardened|cured material (resin layer) of the said resin composition of this invention so that the said metal layer may be covered is preferable. Specifically, (a) film formation process, (b) exposure process, (c) development process, (d) heating process, (e) metal layer formation process, or (a) film formation process , (d) a heating step, and (e) an aspect of repeating the metal layer forming step in this order. By alternately performing the lamination 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 laminated alternately.

(Surface activation treatment process)

The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment.

The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after performing the surface activation treatment step on the resin composition layer after the heating step.

The surface activation treatment may be performed on at least a portion of the metal layer, at least a portion of the resin composition layer after heating, or on at least a portion of both the metal layer and the resin composition layer after heating. 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 where the resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion to the resin composition layer (film) provided on the surface can be improved.

In addition, it is preferable to perform the surface activation treatment also on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to surface activation treatment, adhesion to the metal layer or resin layer provided on the surface of the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as in the case of negative development, it is difficult to receive damage by surface treatment and the adhesion is easy to improve.

As the surface activation treatment, specifically, plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture gas, argon/oxygen mixture gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ After etching treatment by /O ₂ , surface treatment by ultraviolet (UV) ozone method, and immersion in an aqueous hydrochloric acid solution to remove the oxide film, having at least one amino group and thiol group It is selected from an immersion treatment for an organic surface treatment agent containing a compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of 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 .

(Method of manufacturing electronic device)

The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description of paragraphs 0213 to 0218 and the description of FIG. incorporated into the specification.

(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 includes a resin, a compound that generates an acid by irradiation with actinic light or radiation, and a solvent, the resin is a polyimide precursor, and the resin has increased polarity by the action of an acid. It has a group that causes a reaction.

Hereinafter, details of each component included in the resin composition of the present invention will be described.

<Suzy>

The resin composition is a polyimide precursor and contains a resin having a group (polarity converter) that generates a reaction in which polarity is increased by the action of an acid.

Examples of the polarity converter include acid decomposable groups, and groups that are decomposed by the action of acid to generate alkali-soluble groups are 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. From the viewpoint of exposure sensitivity, the acetal group is more desirable.

Among these, the polarity converter is preferably a group represented by the following formula (A-1) or the following formula (A-2).

[Formula 3]

In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * indicates another structure indicates a binding site with;

In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, and at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * is a bond with another structure. indicates the area.

In Formula (A-1), R ^A1 and R ^A2 each 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 hydrogen group, or a group formed by a bond thereof, but a bond between an aliphatic hydrocarbon group and an aliphatic hydrocarbon group and an aromatic hydrocarbon group may be used. is preferably a group represented by, and a group represented by a saturated aliphatic hydrocarbon group or a bond between a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group is preferred.

In formula (A-1), R ^A3 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent hydrocarbon group, more preferably a hydrogen atom.

Further, in formula (A-1), when at least two of R ^A1 to R ^A5 are bonded to form a ring structure, at least one of R ^A1 and R ^A2 and at least one of R ^A3 to R ^A5 are bonded to form a ring structure. It is desirable to form a structure. As a ring structure formed, a tetrahydrofuran ring etc. are mentioned.

In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, preferably a monovalent hydrocarbon group, and more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms; It is more preferable to represent a monovalent hydrocarbon group of 1 to 4 carbon atoms, and it is particularly preferable to represent an alkyl group of 1 to 4 carbon atoms.

When at least two of R ^A6 to R ^A8 are bonded to form a ring structure, the ring structure is not particularly limited, but is preferably an aliphatic hydrocarbon ring structure, more preferably a saturated aliphatic hydrocarbon ring structure.

[Polyimide precursor]

It is preferable that the polyimide precursor used by this invention contains the repeating unit represented by following formula (1).

[Formula 4]

In the above formula (1),

R ¹ represents a tetravalent organic group. A plurality of R ¹ 's may be the same as or different from each other.

R ² represents a divalent organic group. A plurality of R ² may be the same as or different from each other.

R ³ each independently represents a hydrogen atom or an organic group.

The repeating unit represented by Formula (1) preferably contains a polarity converter, and more preferably, at least one of the plurality of -CO ₂ R ³ in Formula (1) is a group containing a polarity converter, It is more preferable that at least one of the plurality of -CO ₂ R ³ in (1) is a group that decomposes under the action of an acid to generate an alkali-soluble group.

Moreover, it is preferable that the repeating unit represented by the said formula (1) contains the group represented by the formula (A-1) or formula (A-2) mentioned above.

When the repeating unit represented by formula (1) contains a group represented by formula (A-1) described above, R ³ in formula (1) is a group represented by formula (A′-1) below, and formula (1) It is preferable that the repeating unit represented by contains the group represented by the above formula (A-1).

Moreover, when the repeating unit represented by Formula (1) contains the group represented by Formula (A-2) mentioned above, by ^R3 being the following formula (A'-2) in Formula (1), Formula (1) It is preferable that the repeating unit represented by contains the group represented by the above formula (A-2).

[Formula 5]

In the formula (A′-1), R ^A1 to R ^A5 each have the same meaning as R ^A1 to R ^A5 in the formula (A-1), and preferred embodiments are also the same. In addition, * represents a bonding site to an oxygen atom to which R ³ in formula (1) bonds.

In the formula (A′-2), R ^A6 to R ^A8 each have the same meaning as R ^A6 to R ^A8 in the formula (A-2), and the preferred embodiments are also the same. In addition, * represents a bonding site to an oxygen atom to which R ³ in formula (1) bonds.

A resin having a repeating unit represented by formula (1) is a resin whose solubility in an alkaline developing solution is increased by the action of an acid. The resin having the repeating unit of Formula (1) is preferably insoluble or sparingly soluble in an alkali developing solution.

The repeating unit represented by formula (1) is a compound having four carboxy groups with R ¹ as a nucleus, a carboxylic acid anhydride, or a group from which hydrogen atoms in at least one of the four carboxy groups are eliminated by the action of an acid. It is composed of an acid component derived from a substituted compound and a diamine component derived from a compound having two amino groups with R ² as a nucleus. In other words, the acid component as a partial structure containing the two carbonyl groups interposed between the two carbonyl groups in Formula (1) and the diamine component as a partial structure represented by -NH-R ² -NH- in Formula (1) It consists of

The tetravalent organic group R ¹ preferably has 4 to 30 carbon atoms, and is more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic or aromatic group. A plurality of R ¹ 's 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 condensed 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, and a cyclohexane ring group.

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- En ventilation, etc. are mentioned.

The tetravalent linking group having a monocyclic or fused polycyclic aliphatic or aromatic group for the tetravalent organic group R ¹ may be the above-mentioned monocyclic or fused polycyclic aliphatic or aromatic group itself, but may be a plurality of monocyclic or condensed polycyclic aliphatic or aromatic groups. Polycyclic aliphatic or aromatic groups may be linked via a single bond or a divalent linking group to form a tetravalent linking group as R ¹ .

As the divalent linking group, 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, an ester bond, a ketone Group, amide group, etc. are mentioned.

Specific examples of the acid component having R ¹ as a nucleus and groups derived from at least four carboxyl groups include pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, and 2,3,3'. ,4'-biphenyltetracarboxylic acid anhydride, 2,2',3,3'-biphenyltetracarboxylic acid anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid anhydride, 2,2',3,3 '-benzophenonetetracarboxylic anhydride, 4,4'-(hexafluoroisopropylidene) iphthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride , 2,3,5,6-pyridinetetracarboxylic acid anhydride, 3,4,9,10-perylenetetracarboxylic acid anhydride, (trifluoromethyl) pyromellitic anhydride, di(trifluoromethyl)pyromellitic acid acid anhydride, di(heptafluoropropyl)pyromellitic anhydride, pentafluoroethylpyromellitic 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'-tetracarboxydiphenyl Methane dianhydride, 3,3',4,4'-tetracarboxydiphenylsulfone 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'-tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4, 4'-tetracarboxydiphenylether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybenzophenone dianhydride, bis[(trifluoromethyl) Dicarboxyphenoxy] benzene dianhydride, 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-dica Components derived from aromatic tetracarboxylic acid anhydrides such as boxyphenoxy)phenyl)hexafluoropropane dianhydride, 5,5'-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride, and cyclobutanetetra carboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetra Carboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, or bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, (1S,2S,4R,5R)-cyclohexanetetracarboxylic dianhydride, (1R,2S,4S,5R)-cyclo and components derived from aliphatic tetracarboxylic acid anhydrides such as hexanetetracarboxylic acid dianhydride.

Preferably, a component derived from pyromellitic anhydride, a component derived from 3,3',4,4'-biphenyltetracarboxylic acid anhydride, and a component derived from 2,3,3',4'-biphenyltetracarboxylic acid anhydride Component derived from 2,2',3,3'-biphenyltetracarboxylic acid anhydride-derived component, 3,3',4,4'-benzophenonetetracarboxylic acid anhydride-derived component, 4,4'-( Hexafluoroisopropylidene) Components derived from iphthalic anhydride, components derived from 3,3',4,4'-tetracarboxydiphenylether dianhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride Component derived from 5,5′-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride, component derived from cyclobutanetetracarboxylic acid anhydride, component derived from cyclopentanetetracarboxylic acid anhydride Components derived from bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, components derived from (1S,2S,4R,5R)-cyclohexanetetracarboxylic dianhydride , It is a component derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, more preferably a component derived from pyromellitic anhydride, 3,3',4,4'-biphenyl Components derived from tetracarboxylic acid anhydride, components derived from 4,4'-(hexafluoroisopropylidene)ifthalic anhydride, components derived from cyclobutanetetracarboxylic acid anhydride, 3,3',4,4'- A component derived from tetracarboxydiphenylether dianhydride, a component derived from cyclopentanetetracarboxylic acid anhydride, a component derived from 5,5′-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride, ( These are components derived from 1S,2S,4R,5R)-cyclohexanetetracarboxylic dianhydride and components derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride. By using these, good solvent solubility, alkali dissolution rate, transparency, and stress characteristics can be realized.

The content in the resin of an acid component derived from a compound having four carboxyl groups with R ¹ as a nucleus is preferably 20 to 70 mol%, and preferably 30 to 60 mol%, based on all repeating units constituting the resin. it is more preferable

R ² in Formula (1) represents a divalent organic group. Examples of the divalent organic group include a straight-chain or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, and examples include a straight-chain or branched aliphatic group of 2 to 20 carbon atoms, a cyclic aliphatic group of 3 to 20 carbon atoms, and a group containing 3 carbon atoms. An aromatic group of ~20 or a group comprising a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, 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.

R ² is preferably derived from diamine. As diamine used for manufacture of the said resin, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine, etc. are mentioned. As for diamine, only 1 type may be used and 2 or more types may be used.

Specifically, it is preferably a diamine containing a group consisting of a straight-chain 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 combination thereof, It is more preferable that it is a diamine containing a C6-C20 aromatic group. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. Examples of the group containing an aromatic group include the following.

[Formula 6]

In the formula, A represents a single bond or a divalent linking group, and 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 combinations thereof, preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)- , -S-, or a group selected from -SO ₂ -, more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or - more preferably C(CH ₃ ) ₂ -.

In the formula, * represents a binding site with another structure.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexyl three; 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 phosphorus 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'-diaminodiphenylsulfone, 4,4'- and 3,3'-di Aminodiphenylsulfide, 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'-diaminoparaterphenyl, 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'-diaminodiphenylsulfone, 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'-tetra Aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-Diamino Biphenyl, 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)octamethylpenta Siloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-di Aminonaphthalene, 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] hexafluoroprop Pain, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoro Ropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-tri Fluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy ) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 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'-hexafluorotolidine and 4 and at least one type of diamine selected from 4'-diamino quaterphenyl.

Moreover, Paragraph 0030 of International Publication No. 2017/038598 - the diamine (DA-1) of 0031 - (DA-18) are also preferable.

Moreover, the diamine which has 2 or more alkylene glycol units of Paragraph 0032 of International Publication No. 2017/038598 - 0034 in a main chain is also used preferably.

R ² is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film. However, Ar is each independently an aromatic group, 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 SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

Moreover, it is preferable that R ^<2> is a divalent organic group represented by following formula (51) or formula (61) from a viewpoint of i-line transmittance. In particular, from the viewpoint of i-line transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

formula (51)

[Formula 7]

In Formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. * indicates a binding site with another structure.

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. can

[Formula 8]

In Formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group. * indicates a binding site with another structure.

Examples of the diamine compound giving the structure of Formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. You may use these by 1 type or in combination of 2 or more types.

Further, in order to improve adhesion to the substrate, a silicon diamine component can be used as a diamine component having R ² as a nucleus. Examples of this include a bis(4-aminophenyl)dimethylsilane component, a bis(4-aminophenyl)tetramethylsiloxane component, a bis(4-aminophenyl)tetramethyldisiloxane component, and bis(γ-aminopropyl) Tetramethyldisiloxane component, 1,4-bis(γ-aminopropyldimethylsilyl)benzene component, bis(4-aminobutyl)tetramethyldisiloxane component, bis(γ-aminopropyl)tetraphenyldisiloxane Ingredients etc. are mentioned.

As a silicon diamine component, the following structure is also mentioned.

[Formula 9]

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, a plurality of R ₇ may be the same as or different from each other. A plurality of R ₈ may be the same as or different from each other.

As the divalent organic group represented by R ₅ and R ₆ , a straight chain or branched alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, or these which may have substituents. A group constituted by combining is shown.

As the monovalent organic group represented by R ₇ and R ₈ , a straight-chain 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 is shown.

More specifically, the following is mentioned.

[Formula 10]

In a specific resin, at least one of a plurality of -CO ₂ R ³ present in the resin is preferably a group that decomposes under the action of an acid to generate an alkali-soluble group.

The group decomposed by the action of an acid to generate an alkali-soluble group is a group that is decomposed by the action of an acid to generate an alkali-soluble group such as a hydroxyl group (eg, phenolic hydroxyl group) or a carboxyl group on the resin side ( Hereinafter, it is also referred to as an acid decomposable group.). In the present invention, the acid-decomposable group is preferably a group that is decomposed by the action of an acid and generates a carboxyl group as an alkali-soluble group on the resin side.

Groups preferable as the acid-decomposable group are groups substituted with groups that release hydrogen atoms of these alkali-soluble groups with acid.

Examples of the group that leaves with an acid include -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 bonded to each other to form a ring.

As said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C5 alkyl group is more preferable.

The alkyl group may be linear or branched.

As said cycloalkyl group, a C3-C12 cycloalkyl group is preferable, and a C3-C8 cycloalkyl group is more preferable.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

It is preferable that the said aryl group is a C6-C30 aromatic hydrocarbon group, and it is more preferable that it is a phenyl group.

As said aralkyl group, a C7-C20 aralkyl group is preferable, and a C7-C16 aralkyl group is more preferable.

The 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-described 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.

Moreover, these groups may further have a well-known substituent within the range in which the effect of this invention is acquired.

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 decomposable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, or an enol ester group. More preferably, it is a tertiary alkyl ester group and an acetal ester group, and a photosensitive film with high sensitivity and high resolution is obtained by using this.

As a tertiary alkyl ester group as an acid-decomposable group, it is preferable that it is an ester group in which the hydrogen atom of a carboxy group was substituted by the group represented by the following formula (AI).

[Formula 11]

In formula (AI),

T represents a single bond or *-Rt-COO-# (* has the same meaning as * in formula (AI), and # represents a bonding 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 each 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 combine to form a cycloalkyl group (monocyclic or polycyclic).

* indicates a binding site with another structure.

Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group, or a -(CH ₂ ) ₃ - group.

Examples of the alkyl group represented by Rx ₁ to Rx ₃ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, hexyl, octyl, and dodecyl groups having 1 to carbon atoms; An alkyl group of 20 is preferable, and an alkyl group of 1 to 6 carbon atoms is more preferable.

The cycloalkyl group represented by Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. do.

Examples of the cycloalkyl group formed by combining 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 group. A cycloalkyl group of the ring is preferred. A monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferred.

In Formula (AI), an embodiment in which 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 is preferable.

Each said group may have a substituent, and as a substituent, an alkyl group (C 1-4), a halogen atom, a hydroxyl group, an alkoxy group (C 1-4), a polyalkyleneoxy group, a carboxy group, for example, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably having 20 or less carbon atoms.

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.

In specific examples, Rxa and Rxb each represent an alkyl group having 1 to 6 carbon atoms. Z represents the substituent which said each group may have, and when it exists in multiple numbers, it is respectively independent. p represents 0 or a positive integer. * indicates a binding site with another structure.

[Formula 12]

[Formula 13]

The tertiary alkyl ester group as the acid-decomposable group is a group represented by formula (AI) and is a tertiary alkyl ester group having at least either one of a group represented by the following formula (I) and a group represented by the following formula (II) more preferable

[Formula 14]

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 necessary for forming an alicyclic structure together with a carbon atom.

* indicates a binding site with another structure.

The alkyl group in R ₂ may be straight-chain or branched, and may have a substituent.

The cycloalkyl group for R ₂ may be monocyclic or polycyclic, and may have a substituent.

R ₂ 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 necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and more preferably a hydrocarbon ring structure. The number of carbon atoms in the monocyclic alicyclic structure or hydrocarbon ring structure is preferably 3 to 8, more preferably 5 or 6.

The alkyl group in R ₄ , R ₅ , and R ₆ may be straight-chain or branched, and may have a substituent. As an alkyl group, C1-C6 things, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and a hexyl group, are preferable.

The cycloalkyl group for R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic, and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

As group represented by formula (I), group represented by following formula (I-a) and (I-b) is mentioned, for example.

[Formula 15]

In the formula, R ₂ has the same meaning as R ₂ in the formula (I).

* indicates a binding site with another structure.

The group represented by formula (II) is preferably a group represented by formula (II-a) below.

[Formula 16]

In formula (II-a),

R ₄ and R ₅ have the same meaning as those in formula (II).

* indicates a binding site with another structure.

As an acetal ester group as an acid-decomposable group, it is preferable that it is an ester group in which the hydrogen atom of a carboxy group was specifically substituted by the group represented by following formula (III).

[Formula 17]

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 hetero atom, or an aromatic ring group which may contain a hetero atom.

At least two of Ra, Rb, and Q may be bonded to each other to form a ring. It is preferable that this ring is a 5-membered ring or a 6-membered ring.

* indicates a binding site with another structure.

The alkyl group, cycloalkyl group, aryl group or aralkyl group as Ra includes the same as those described above as the alkyl group, cycloalkyl group, aryl group or aralkyl group for R ₃₆ .

It is also preferable that Ra is a group represented by the following formula (IV) or (V) from the viewpoint of suppressing decomposition of the acetal ester group as an acid-decomposable group during storage by steric hindrance and preventing a decrease in patterning properties.

[Formula 18]

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, a cyano group, or 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.

* indicates a binding site with another structure.

When Ra is a group represented by formula (IV) or formula (V), in a resin having a repeating unit represented by formula (1), progress of the imidation reaction during storage can be suppressed, and a decrease in patterning properties can be prevented. there is.

Examples of the alkyl, cycloalkyl, aryl, or aralkyl groups for Rc, Rd, Re, Rf, and Rg are the same as those described above as the alkyl, cycloalkyl, aryl, and aralkyl groups for R ₃₆ .

As an alkoxy group as Rc, Rd, Re, Rf, or 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.

Moreover, any of linear, branched chain, or cyclic|annular may be sufficient as the alkyl group part in the said alkoxy group, and the aspect which combined these may be sufficient as it.

As the aryloxy group for Rc, Rd, Re, Rf, or Rg, an aryloxy group having 6 to 10 carbon atoms is preferable, and phenoxy, toluyloxy, 1-naphthoxy, etc. are specifically mentioned.

As the alkoxycarbonyl group for Rc, Rd, Re, Rf, or Rg, an alkoxycarbonyl group having 1 to 10 carbon atoms is preferable, and specifically, methoxycarbonyl, ethoxycarbonyl, straight-chain or branched propoxycarbonyl, and cyclopentyl. Oxycarbonyl, cyclohexyloxycarbonyl, etc. are mentioned.

Examples of the aryloxy moiety of the aryloxycarbonyl group as Rc, Rd, Re, Rf, and Rg are the same as those of the aryloxy group described above.

At least one of Rc and Rd in formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, It is preferable that they are an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and it is more preferable that 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, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), cyclo An alkylene 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 thereof, 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, a hexyl group, an octyl group, etc. )am.

Rb is preferably a single bond, an alkylene group, or a divalent linking group composed of a combination of at least one of an alkylene group and -O-, -CO-, -CS- and -N(R ₀ )-, and a single bond, an alkylene group, A divalent linking group consisting of a combination of a rene group or an alkylene group and -O- is more preferred. Here, R ₀ has the same meaning as the above-mentioned R ₀ .

The alkyl group as Q is, for example, the same as the alkyl group as Ra described above.

Examples of the alicyclic group and aromatic ring group as Q include the cycloalkyl group and aryl group as Ra described above. The carbon number is preferably 3 to 18. In the present invention, a group formed by connecting a plurality of aromatic rings via a single bond (for example, a biphenyl group or a terphenyl group) is also included in the aromatic group as Q.

As an alicyclic group containing a hetero atom and an aromatic ring group containing a hetero atom, for example, thylane, cyclothiolein, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imimi dazoles, benzimidazoles, triazoles, thiadiazoles, thiazoles and pyrrolidones.

The alicyclic group and aromatic ring group as Q may have a substituent, and examples thereof include 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.

Especially preferably, (-Rb-Q) is a methyl group, an aryloxyethyl group, a cyclohexylethyl group, or an arylethyl group, and solubility and thermal stability are improved.

When at least two of Ra, Rb, and Q are bonded to each other to form a ring, for example, any one of Rb and Q is bonded to Ra to form a propylene group or a butylene group, and a 5-membered ring containing an oxygen atom Or the case of forming a 6-membered ring is mentioned.

If the total number of carbon atoms of Ra, Rb, and Q is expressed as N _C , when N _C is large, the change in the alkali dissolution rate of the resin before and after the group represented by formula (III) is desorbed becomes large, and the dissolution contrast becomes high. and the resolution is improved. The range of N _C is preferably 2 to 20, particularly preferably 2 to 15. When N _C is 20 or less, a decrease in the glass transition temperature of the polymer compound is suppressed, and generation of defects in which products desorbed from acid-decomposable groups adhere on patterns is suppressed.

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. In this way, in the resin having the repeating unit represented by Formula (1), decomposition of the acid-decomposable group during storage can be suppressed, and deterioration in patterning properties can be prevented.

As an electron withdrawing group, for example, 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, a nitrile group (between ano group), an alkyl sulfonyl group, an aryl sulfonyl group, a nitro group, and the like, and an alkoxy group, an aryl group, and an acyl group are preferable.

Although the specific example of the group represented by Formula (III) which comprises the acetal ester group as an acid-decomposable group below is shown, it is not limited to these. * indicates a binding site with another structure.

[Formula 19]

[Formula 20]

[Formula 21]

The thermal decomposition temperature of -CO ₂ R ³ in Formula (1) is preferably 100 to 220°C, more preferably 120 to 210°C, and particularly preferably 140 to 200°C. The thermal decomposition temperature can be obtained from, for example, differential thermal balance analysis.

When the thermal decomposition temperature is equal to or higher than the lower limit, the storage stability of the resin composition of the present invention is improved. Moreover, the exposure sensitivity of the resin composition of this invention improves that a thermal decomposition temperature is below the said upper limit.

Specifically, as the structure of R ³ capable of achieving the thermal decomposition temperature as described above, at least one of Rx ₁ to Rx ₃ in the formula (A1) is a group represented by the following formula (VI), the formula (III ) in which Ra is a group represented by the above formula (IV) or the following formula (VII); and the like.

[Formula 22]

In the formula (VI), each of R ₇ to R ₈ independently represents a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic), and at least one of R ₇ to R ₈ is a hydrogen atom. . * indicates a binding site with another structure.

[Formula 23]

In the 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. * indicates a binding site with another structure.

Specific examples and preferred examples of the alkyl group and cycloalkyl group for R ₇ to R ₈ include the same specific examples and preferred examples as the alkyl group and cycloalkyl group for Rx ₁ to Rx ₃ described above.

Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rh include those described above as the alkyl group, cycloalkyl group, aryl group, or aralkyl group for R ₃₆ .

As an alkoxy group as Rh, a C1-C20 alkoxy group is preferable, and a C1-C6 alkoxy group is more preferable.

Moreover, any of linear, branched chain, or cyclic|annular may be sufficient as the alkyl group part in the said alkoxy group, and the aspect which combined these may be sufficient as it.

As the aryloxy group as Rh, an aryloxy group having 6 to 10 carbon atoms is preferable, and phenoxy, toluyloxy, 1-naphthoxy, etc. are specifically mentioned.

As the alkoxycarbonyl group for Rh, an alkoxycarbonyl group having 1 to 10 carbon atoms is preferable, and specifically, methoxycarbonyl, ethoxycarbonyl, straight-chain or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl Neil et al.

Examples of the aryloxy moiety of the aryloxycarbonyl group as Rh include the same as the aryloxy group described above.

In addition, R ³ in Formula (1) may be an organic group different from a group that is decomposed by the action of an acid to generate an alkali-soluble group.

As such an organic group, it can be used without particular limitation within the range in which the effects of the present invention can be obtained, but a straight-chain or branched-chain alkyl group, a cycloalkyl group, an aryl group, or a polyalkyleneoxy group is exemplified. Preferred aspects of these groups are the same as those for these groups for R ₃₆ described above.

In the present invention, a hydrogen atom and an organic group may be mixed in R ³ . It is preferable that the ratio of organic groups is 100 mol% - 20 mol% with respect to all ^R3 in resin, and it is more preferable that the ratio of organic groups is 100 mol% - 40 mol% organic groups. By adjusting the amount of hydrogen atoms and organic groups of this R ³ , the dissolution rate in aqueous alkali solution changes, so that a resin composition having an appropriate dissolution rate can be obtained by this adjustment.

Among all -CO ₂ R ³ in the resin, the ratio occupied by groups generating alkali-soluble groups by decomposition by the action of acid, so-called protection rate, is preferably 40 to 100%, more preferably 45 to 100%.

Moreover, in this invention, the terminal blocker can be made to react with the terminal of the polymer which has the repeating unit represented by Formula (1) as a main component. As the terminal blocker, monoalcohols, phenols, thiols, thiophenols, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds and the like can be used. By reacting the end capping agent, the number of repetitions of the repeating unit, that is, the molecular weight can be controlled within a preferred range, which is preferable. In addition, the acid deactivation due to neutralization of the terminal amine and the generated acid can be suppressed by the terminal blocker. In addition, various organic groups such as crosslinking reactive groups having carbon-carbon unsaturated bonds can be introduced as terminal groups by reacting terminal end capping agents.

As the monoalcohol used for the end capping agent, methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol Primary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol, etc., secondary alcohols such as t-butyl alcohol, tertiary alcohols such as adamantane alcohol can be heard Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene.

The monoamine used for the end capping agent is 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-carboxy-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, ammelide, 2-aminobenzoic acid, 3- Aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3- Aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 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-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-a Minonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercapto pyrimidine, 2-aminothiophenol, 3-aminothiophenol , 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2 ,6-Diethynylaniline, 3,4-Diethynylaniline, 3,5-Diethynylaniline, 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-diethynyl-1-aminonaphthalene, 3,5 -Diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1- Aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, aniline, etc. However, it is not limited to these.

Among 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-amino Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyr Midine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynyl Aniline, 3,4-diethynylaniline, 3,5-diethynylaniline, aniline, etc. are preferable.

Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as terminal blockers are acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic anhydride. , 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy Roxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy Roxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mer Capto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2- Ethanylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3 ,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid Tosan, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethyne 1-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid , 7-ethynyl-2-naphthoic acid, monocarboxylic acids such as 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxy groups are acid chlorides, and terephthalic acid, phthalic acid, maleic acid, cyclohexyl Seindicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5- Dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxy Monoacid chloride compounds and monoacid chloride compounds in which only the monocarboxy groups of dicarboxylic acids such as cinaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are acid chlorides Active ester compounds obtained by reaction of N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboximide, and the like are exemplified.

Among these, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride and 3-hydroxyphthalic 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-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diene Monocarboxylic acids such as tyneylbenzoic acid and 3,5-diethyinylbenzoic acid, and monoacid chloride compounds in which these carboxy groups are acid chlorides, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxylic acid Monoacid chloride compounds and monoacid chloride compounds in which only the monocarboxy groups of dicarboxylic acids such as carboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene are acid chlorides An active ester compound obtained by reaction of N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide is preferable.

The introduction ratio of the monoamine used in the end capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine components. The introduction ratio of a compound selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as end capping agents is preferably in the range of 0.1 to 100 mol%, particularly preferably, with respect to the diamine component. It is 5-90 mol%. A plurality of different terminal groups may be introduced by reacting a plurality of end capping agents.

The terminal blocker introduced into the polymer can be easily detected by the following method. For example, a polymer into which an end capping agent is introduced is dissolved in an acidic solution to decompose into an amine component and an acid anhydride component, which are constituent units of the polymer. The terminal capping agent can be easily detected by gas chromatography (GC) or NMR measurement. In addition, it can be easily detected also by direct thermal decomposition gas chromatography (PGC) or infrared spectrum and ¹³ CNMR spectrum measurement of the polymer component into which the end capping agent has been introduced.

It is preferable that the specific resin used for the resin composition of this invention has as a main component the repeating unit represented by Formula (1). A main component here means containing 70 mol% or more of the repeating unit represented by Formula (1). More preferably, it is 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 Formula (1) and another repeating unit, or may be a mixture of a plurality of resins containing a repeating unit represented by Formula (1).

Furthermore, a resin containing a repeating unit represented by formula (1) and a resin not containing a repeating unit represented by formula (1) (for example, in formula (1), R ³ is decomposed by the action of an acid) and a resin having no group generating an alkali-soluble group) may be used. In this case, it is preferable to contain 50 mass % or more, and, as for resin containing the repeating unit represented by Formula (1), it is more preferable to contain 75 mass % or more.

The type and amount of repeating units used for 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 Formula (1) preferably has a mass average molecular weight of 200,000 or less, more preferably 1,000 to 200,000, and even more preferably 2,000 to 100,000, in terms of alkali dissolution rate, film properties, and the like. And, 3,000 to 100,000 is particularly preferred. By setting the molecular weight within this range, a photosensitive film having low stress, excellent mechanical properties, and excellent resolution with fewer development defects can be obtained.

The degree of dispersion (molecular weight distribution) is preferably 1.0 to 7.0, and more preferably 1.5 to 6.5.

In this specification, degree of dispersion is a value calculated by weight average molecular weight/number average molecular weight.

Moreover, when a resin composition contains multiple types of specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least 1 sort(s) of specific resin are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the dispersion degree calculated as one resin of the said plurality of types of specific resin are each within the said range.

As the method for producing the specific resin in the present invention, any conventionally known method may be used (for example, see Latest Polyimide -Basics and Applications- (Japanese Polyimide Research Society edition)).

For example, in the case of polyamide acid or polyamide acid ester, a method of reacting tetracarboxylic acid dianhydride and a diamine compound at low temperature, obtaining a diester by tetracarboxylic acid dianhydride and alcohol, and then the presence of an amine and a condensing agent a method of reacting with tetracarboxylic acid dianhydride and an alcohol to obtain a diester, then converting the remaining dicarboxylic acid into an acid chloride and reacting with an amine, imidizing a part of the carboxy group of the side chain by heat treatment, or , a method of alkyl esterification using an esterification reagent or the like.

Among them, polyamide acid is obtained by reacting a diamine compound and tetracarboxylic dianhydride at -20 to 50 ° C. for several minutes to several days in an organic solvent, followed by reaction with basic halides or acidic vinyl ethers A method for obtaining a resin containing a repeating unit represented by formula (1) by a reaction with or a reaction of dimethylformamide with a dialkyl acetal (synthetic method 1), also Makromol. Chem., 194, 511 to 521 (1993) synthesizes a dicarboxylic acid having an acid-decomposable group, followed by polycondensation with diamine (synthetic method 2), in terms of cost, ease of operation, and reproducibility of performance. preferred in terms of

(Synthetic method 1)

[Formula 24]

(Synthetic method 2)

[Formula 25]

In the above scheme, R ¹ , R ² and R ³ have the same meaning as those in formula (1).

Examples of organic solvents that can be used in the synthesis reaction of polyamide acid include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl- Amide solvents such as 2-imidazolidinone, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, aromatic solvents such as pyridine, chloroform, dichloromethane, 1,2-di Halogen solvents such as chloroethane and 1,1,2,2-tetrachloroethane; ether solvents such as tetrahydrofuran, dioxane and diglyme; and the like can be exemplified. Among them, amide-based solvents are preferable, and specific resins 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.

A resin composition containing a 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), a relief pattern can be formed by a subsequent exposure process and developing process. By the heat treatment of this pattern, dehydration ring closure of a specific resin occurs, and a cured polyimide is obtained.

In the present invention, the specific resin has an i-line transmittance of 1% or more, preferably 5% or more, more preferably 10% or more, and 10 to 80% per film thickness of the film formed of the specific resin. particularly preferred. When this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern with high resolution and good shape. Transmittance of i-line (light with a wavelength of 365 nm) can be measured with a spectrophotometer (for example, Hitachi U3410 model, manufactured by Hitachi Seisakusho Co., Ltd.).

Further, the residual stress of the cured polyimide product formed by imide ring closure from the polyamide acid ester having the repeating unit represented by the above formula (1) is preferably 35 MPa or less, and more preferably 30 MPa or less.

In addition, the residual stress of the polyimide film can be measured at room temperature (25°C) with 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) that satisfies these characteristics can have a rigid and straight main chain in which the aromatic ring π-conjugate length is suppressed, for example, by selecting an appropriate raw material at the time of synthesizing the resin. It has a structure that can be formed.

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, still more preferably 40% by mass or more, and 50% by mass with respect to the total solid content of the resin composition. More than that is more preferable. 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, still more preferably 98% by mass or less, and 97% by mass or less with respect to the total solid content of the resin composition. It is more preferable that it is mass % or less, and it is still more preferable that it is 95 mass % or less.

Moreover, in this invention, specific resin may be used by 1 type, and may use a plurality together.

<Other resins>

The resin composition of the present invention may also contain the specific resin described above and another resin different from the specific resin (hereinafter, simply referred to as “other resin”).

Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, A polyether resin, a polyester resin, etc. are mentioned.

For example, by further adding a (meth)acrylic resin, a resin composition excellent in applicability is obtained, and a pattern (cured product) excellent in solvent resistance is obtained.

For example, instead of the polymerizable compound described later or in addition to the polymerizable compound described later, the weight average molecular weight has a high polymerizable value of 20,000 or less (for example, the molar amount of the polymerizable group in 1g of the resin is 1 × 10 ⁻³ mol/g or more) (meth)acrylic resin can be added to the resin composition to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), and the like.

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, more preferably 0.05% by mass or more, and still more preferably 1% by mass or more with respect to the total solid content of the resin composition. It is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably, and even more preferably 10% by mass or more.

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, still more preferably 70% by mass or less, with respect to the total solid content of the resin composition. , it is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

Moreover, as a preferable aspect of the resin composition of the present invention, an aspect in which the content of other resins is low is also possible. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and preferably 5% by mass or less with respect to the total solid content of the resin composition. It is still more preferable, and it is still more preferable that it is 1 mass % or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.

The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

[mine generator]

The resin composition of the present invention contains a photoacid generator.

A photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. Light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. In the case where the photoacid generator is used alone or in combination with a sensitizer, it is preferably a photoacid generator capable of generating an acid by photosensitization.

Examples of acids generated 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, sulfonamide, etc. may be preferred.

Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.

From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and oxime esters are preferred from the viewpoint of the mechanical properties of the formed film.

Examples of the quinonediazide compound include those in which sulfonic acid of quinonediazide is ester bonded to a monovalent or polyvalent hydroxy compound, those in which sulfonic acid of quinonediazide is sulfonamide bonded to a monovalent or polyvalent amino compound, and polyhydroxypolyamino compounds and those in which sulfonic acid of quinonediazide is bonded to an ester bond and/or a sulfonamide bond. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds do not have to be substituted with quinonediazide, but it is preferable that 40 mol% or more of the total functional groups on average are substituted with quinonediazide. . By containing such a quinonediazide compound, a resin composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are general ultraviolet rays, can be obtained.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4 HBPA , 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, Methylentris-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 (above, brand name, manufactured by Honshu Kagaku High School), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4 PC, BIR -BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade names, manufactured by Asahi Yukizai Kogyo), 2,6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name , Honshu Chemical Co., Ltd.), novolak resin, etc., but are not limited thereto.

Specifically as amino compounds, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.

In addition, specific examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine. not limited to these

Among these, as a quinonediazide compound, what contains the ester of a phenol compound and 4-naphthoquinone diazide sulfonyl group is preferable. 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, based on 100 parts by mass of the resin. By making content of a quinonediazide compound into this range, when contrast of an exposed part and an unexposed part is obtained, since higher sensitivity can be aimed at more, it is preferable. You may further add a sensitizer etc. as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, 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 is represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105). It is preferable that it is an oxime sulfonate compound shown.

[Formula 26]

In Formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X ³ are present, they may be the same or different. The alkyl group and alkoxy group in X ³ may have a substituent. As the alkyl group for X ³ , a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group for X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As a halogen atom in said X ^<3> , a chlorine atom or a fluorine atom is preferable.

In Formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.

In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, and is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogen having 1 to 5 carbon atoms. It is preferably a substituted alkoxy group, 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, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms , an aryl group having 6 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, X ³ is a methyl group, the substituted position of X ³ is an ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, and 7,7-dimethyl-2- A compound having an oxonobonylmethyl group or a p-tolyl group is particularly preferred.

As a specific example of the oxime sulfonate compound represented by Formula (OS-1), the following compounds described in Paragraph Nos. 0064-0068 of Unexamined-Japanese-Patent No. 2011-209692 and Paragraph No. 0158-0167 of Unexamined-Japanese-Patent No. 2015-194674 are illustrated. and these contents are incorporated herein.

[Formula 27]

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 thereof, is each independently a hydrogen atom, an alkyl group, an aryl group, or a Represents a rosen atom, R ^s6 , which may exist in plural numbers, each 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, and ms represents an integer from 0 to 6.

In formulas (OS-103) to (OS-105), an alkyl group (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), or a heteroaryl group (preferably 4 to 30 carbon atoms) represented by R ^s1 This preferable) may have a known substituent within the range in which the effect of this invention is acquired.

In 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), and hydrogen It is more preferably an atom or an alkyl group. Among R ^s2 that may exist in two or more in a compound, one or two are preferably an alkyl group, an aryl group, or a halogen atom, more preferably one is an alkyl group, an aryl group, or a halogen atom, and one is an alkyl group , and it is particularly preferred that the remainder are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a known substituent within the range where the effect of the present invention is obtained.

In Formula (OS-103), Formula (OS-104), or 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 reduction is a 5- or 6-membered ring.

In 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 2 desirable.

In formulas (OS-103) to (OS-105), the alkyl group (preferably 1 to 30 carbon atoms) and the alkyloxy group (preferably 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.

In 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, particularly preferably 0.

In addition, the compound represented by the formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the formula (OS-104 ) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) Compounds are particularly preferred.

[Formula 28]

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 1 to 10 carbon atoms. 8 represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 is represents a hydrogen atom or a methyl group.

In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

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, a phenyl group, or Represents a chlorophenyl group, preferably an alkyl group, a halogen atom or a phenyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly a methyl group desirable.

In 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.

Moreover, in the said oxime sulfonate compound, about the three-dimensional structure (E, Z) of an oxime, either one may be sufficient and a mixture may be sufficient as it.

As a specific example of the oxime sulfonate compound represented by the said Formula (OS-103) - Formula (OS-105), Paragraph No. 0088 of Unexamined-Japanese-Patent No. 2011-209692 - 0095, Paragraph No. 0168 - of Unexamined-Japanese-Patent No. 2015-194674 - The compounds described in 0194 are exemplified, and these contents are incorporated herein by reference.

As another suitable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by the following formula (OS-101) and formula (OS-102) is mentioned.

[Formula 29]

In Formula (OS-101) or Formula (OS-102), R ^u9 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, or a cyano group. group, aryl group or heteroaryl group. An aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and an aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is still more preferable.

In formula (OS-101) or formula (OS-102), R ^u2a 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 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In Formula (OS-101) or Formula (OS-102), R ^u1 to R ^u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, represents an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an 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 condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 bond to each other to form an aryl group is also preferable. Among them, an aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the substituents described above may further have a substituent.

It is more preferable that the compound represented by the formula (OS-101) is a compound represented by the formula (OS-102).

Moreover, in the said oxime sulfonate compound, about the steric structure (E, Z, etc.) of an oxime and a benzothiazole ring, either one may be sufficient respectively, and a mixture may be sufficient as it.

As a specific example of the compound represented by formula (OS-101), Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2011-209692 - 0106, and Paragraph No. 0195 of Unexamined-Japanese-Patent No. 2015-194674 - the compound of 0207 are illustrated, These contents are incorporated herein by reference.

Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferable.

[Formula 30]

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 Chemical Co., Ltd.), and the like. .

Moreover, the compound represented by the following structural formula is also mentioned as a preferable example.

[Formula 31]

As an organic halogenated compound, specifically, Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Laid-Open Patent Publication 55-32070, Japanese Laid-Open Patent Publication 60-239736, Japanese Laid-Open Patent Publication 61-169835, Japanese Laid-Open Patent Publication 61-169837, Japanese Laid-Open Patent Publication 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, M. P. Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970 ), and the like, the contents of which are incorporated herein by reference. In particular, oxazole compounds in which a trihalomethyl group is substituted: S-triazine compounds are exemplified as preferred examples.

More preferably, s-triazine derivatives in which at least one mono, di, or trihalogen substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (monochloro Methyl) -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-epoxyphenyl)-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-(p-i-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tri Azine, 2-(4-nathoxynaphthyl)-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 (tribe lomomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc. can be heard

As an organic borate compound, Unexamined-Japanese-Patent No. 62-143044, Unexamined-Japanese-Patent No. 62-150242, Unexamined-Japanese-Patent No. 9-188685, Unexamined-Japanese-Patent No. 9-188686, Japan, for example Japanese Unexamined Patent Publication No. 9-188710, Japanese Unexamined Patent Publication No. 2000-131837, Japanese Unexamined Patent Publication No. 2002-107916, Japanese Patent Publication No. 2764769, Japanese Unexamined Patent Publication No. 2002-116539, etc., and Kunz, Martin " Rad Tech '98. Proceeding April 19-22, 1998, Chicago" and the like, organic borates described in Japanese Unexamined Patent Publication No. Hei 6-157623, Japanese Unexamined Patent Publication No. Hei 6-175564, Japanese Unexamined Patent Publication No. Hei 6-175561 The organic boron sulfonium complex or organoboron oxosulfonium complex described in, Japanese Unexamined Patent Publication No. 6-175554, Organic boron iodonium complex described in Japanese Unexamined Patent Publication No. Hei 6-175553, Japanese Unexamined Patent Publication Hei 9- 188710, an organoboron phosphonium complex described in Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527, Organoboron transition metal coordination complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are mentioned as a specific example, These content is integrated in this specification.

As a disulfone compound, the compound and diazodisulfone compound described in Unexamined-Japanese-Patent No. 61-166544, Japanese Patent Application No. 2001-132318, etc. are mentioned.

As the onium salt compound, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18,387 (1974), T. S. Bal et al, Polymer, 21,423 (1980) diazonium salts, US Patent Publication No. 4,069,055, ammonium salts described in Japanese Unexamined Patent Publication Hei 4-365049, etc., US Patent Publication No. 4,069,055 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, each specification of No. 410,201, Japanese Unexamined Patent Publication No. 2-150848, Japanese Unexamined Patent Publication Hei 2 Iodonium salt described in -296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, 339,049 , 4,760,013, 4,734,444, 2,833,827, German Patent Publication Nos. 2,904,626, 3,604,580, and 3,604,581 sulfonium salts, J. V. Crivello et al, Macromolecules, 10(6), 1307 (1977) , J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17,1047 (1979) selenium salts, C. S. Wen et al, Teh, Proc. Conf. Rad. and onium salts such as arsonium salts and pyridinium salts described in Curing ASIA, p478 Tokyo, Oct (1988), and the like, and the names of these are incorporated herein by reference.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

[Formula 32]

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 preferable substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, and a carbon atom group of 2 to 12 carbon atoms. an alkynyl group, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, An alkylamide group having 1 to 12 carbon atoms in an alkyl group or an arylamide group having 6 to 20 carbon atoms in an aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a carbon number 1 to 12 The thioaryl group of 12 is mentioned. Z ₁₁ ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and in terms of stability A perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, and a sulfinic acid ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group of 1 to 12 carbon atoms and an alkene of 2 to 12 carbon atoms. Diary, C2-12 alkynyl group, C1-12 aryl group, C1-12 alkoxy group, C1-12 aryloxy group, halogen atom, C1-12 monoalkylamino group, alkyl group A dialkylamino group having 1 to 12 carbon atoms each independently, an alkylamide group or arylamide group having 1 to 12 carbon atoms in the alkyl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a cyano group having 1 to 12 carbon atoms An oalkyl group and a thioaryl group having 1 to 12 carbon atoms are exemplified. Z ₂₁ ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, and a sulfate ion, and has stability and reactivity. For cotton, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , R ₃₃ each independently represent an aryl group or alkyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, an alkenyl group, or an alkynyl group, preferably From the viewpoint of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an alkynyl group of 2 to 12 carbon atoms, an aryl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, and an aryloxy group of 1 to 12 carbon atoms. Group, halogen atom, monoalkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms in the alkyl group independently, alkylamide group or arylamide group having 1 to 12 carbon atoms in the alkyl group, 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, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, and a sulfate ion, and has stability and reactivity. For cotton, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

Specific examples of preferable photoacid generators include the following.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably in an amount of 0.5 to 18% by mass, more preferably in an amount of 0.5 to 10% by mass, and preferably in an amount of 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferable to use 3% by mass, and it is even more preferable to use 0.5 to 1.2% by mass.

A photoacid generator may be used individually by 1 type, and may be used in the combination of multiple types. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.

Moreover, in order to impart photosensitivity with respect to a desired light source, it is also preferable to use together with a sensitizer.

<Solvent>

The resin composition of the present invention contains a solvent.

A well-known solvent can be used arbitrarily as a solvent. 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.

As esters, for example, 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, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxy methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., 3-alkyloxymethylpropionate, 3-alkyloxy Ethyl propionate and the like (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (eg For example, 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, Ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are mentioned as suitable ones.

As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Lycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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, Propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene Glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are mentioned as suitable ones.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like. can

As the cyclic hydrocarbons, suitable examples thereof include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.

As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable one.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetyl Morpholine etc. are mentioned as a suitable thing.

As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. are mentioned as suitable ones.

As alcohols, 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 Colmonomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono Phenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, etc. are mentioned.

As for the solvent, a form in which two or more types are mixed is also preferable from the viewpoint of improving the properties of the coated surface.

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-heptane one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One solvent selected from propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

The content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, from the viewpoint of applicability. It is more preferable to set it to 70 mass %, and it is more preferable to set it as 20 to 70 mass %. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and a coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types of solvents. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

<Diffusion scavenger>

The resin composition of the present invention preferably contains an acid trapping agent in order to reduce the change in performance over time from exposure to heating. Here, the acid scavenger refers to a compound capable of trapping a generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable. And, secondary amines, tertiary amines, and ammonium salts are more preferable.

As the acid scavenger, 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 ether bond, and a hydroxyl group and/or ether bond aniline derivatives having When it has an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator. it is desirable

Examples of the acid trapping agent having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the acid trapping agent having a diazabicyclo structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1, 8-diazabicyclo[5,4,0]undec-7-ene etc. are mentioned. As the acid scavenger having an onium structure, tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide oxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. can be heard Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the acid trapping agent having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the acid trapping agent having a pyridine structure include pyridine and 4-methylpyridine. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. As an aniline derivative which has a hydroxyl group and/or ether bond, N,N-bis (hydroxyethyl) aniline etc. are mentioned.

Specific examples of preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethyl Amine, 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, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2 -Dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazole zoline, aminomorpholine, aminoalkylmorpholine and the like.

These acid trapping agents may be used individually by 1 type, or may be used in combination of 2 or more types.

The composition according to the present invention may or may not contain a dust trapping agent, but when it is contained, the content of the dust trapping agent is usually 0.001 to 10% by mass based on the total solids of the composition, preferably. is 0.01 to 5% by mass.

The use ratio of the acid generator and the acid scavenger is preferably acid generator/sand 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 with the passage of time from exposure to heat treatment. The acid generator/dispersion complexing agent (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

<Heat curing accelerator>

The resin composition may also contain a thermosetting accelerator.

Examples of the thermal curing accelerator include thermal polymerization initiators and thermal acid generators.

When the resin composition contains a radical crosslinking agent as a polymerizable compound, a thermal polymerization initiator is included, and when it contains another crosslinking agent, an aspect including a thermal acid generating agent is exemplified.

[Thermal polymerization initiator]

As the thermal polymerization initiator, a thermal radical polymerization initiator may be particularly included. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned, This content is integrated in this specification.

When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass with respect to the total solid content of the resin composition of the present invention. is mass %. The thermal polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of thermal polymerization initiators, it is preferable that the total amount is the said range.

[thermal acid generator]

The resin composition may also contain a thermal acid generator.

The thermal acid generator generates an acid by heating and causes a crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound. has a stimulating effect.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, acid is not generated during drying (prebaking: about 70 to 140° C.) after coating the composition on a substrate, and at the time of final heating (curing: about 100 to 400° C.) after patterning by subsequent exposure and development. Selecting an acid-generating agent as the thermal acid generator is preferable because the decrease in sensitivity during development can be suppressed.

The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak having the lowest temperature when the thermal acid generator is heated up to 500°C at 5°C/min in a pressure-resistant capsule.

Q2000 (made by TA Instruments) etc. are mentioned as a device used when measuring the thermal decomposition start temperature.

The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. Haloalkylsulfonic acids, such as phonic acid or trifluoromethanesulfonic acid, etc. are preferable. As an example of such a thermal acid generator, the thing of Unexamined-Japanese-Patent No. 2013-072935 Paragraph 0055 is mentioned.

Among them, it is more preferable to generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms from the viewpoint of less residual in the cured product (cured film) and less difficulty in reducing the physical properties of the cured product (cured film). and methanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonic acid benzyl (4-hydroxyphenyl) Methylsulfonium, Methanesulfonate Benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, Methanesulfonate(4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, Trifluoro Romethenesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4 -Hydroxyphenyl) methylsulfonium, trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl (( 2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-iridene)-2-(o-tolyl)propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane is preferable as the thermal acid generator.

Moreover, the compound of Paragraph 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid 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. Since the crosslinking reaction is accelerated by containing 0.01 part by mass or more, the mechanical properties and solvent resistance of the cured product (cured film) can be further improved. Moreover, from a viewpoint of the electric insulating property of hardened|cured material (cured film), 20 mass parts or less is preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are still more preferable.

<Base generator>

The resin composition of the present invention may also contain a base generator. Here, a base generator is a compound capable of generating a base by 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 cyclization resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be accelerated by, for example, heating, and the mechanical properties and chemical resistance of the cured product are improved, for example, for a redistribution layer included in a semiconductor package. The performance as an interlayer insulating film becomes good.

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 known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, and nitrobenzylcarbamate compounds. , sulfonamide compound, imidazole derivative compound, amineimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, quaternary ammonium salt derivative compound, pyridinium salt, α-lactone ring derivative compound, amineimide compound, phthal Imide derivative compounds, acyloxyimino compounds and the like can be used.

As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned.

[Formula 37]

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, there is no case where Rb ¹ and Rb ² simultaneously become a hydrogen atom. In addition, none of Rb ¹ , Rb ² and Rb ³ have a carboxy group. In addition, in this 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, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited thereto.

In formulas (B1) and (B2), as for Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of these includes a cyclic structure, and it is more preferable that at least two of these include a cyclic structure. As the cyclic structure, either a monocycle or a condensed ring may be used, and a monocycle or a condensed ring in which two monocycles are condensed is preferable. A 5-membered ring or a 6-membered ring is preferable, and, as for a monocyclic ring, a 6-membered ring is preferable. As for a monocyclic ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, , 2 to 18 are more preferred, 3 to 12 are more preferred), an aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), or an arylalkyl group ( It is preferably 7 to 25 carbon atoms, more preferably 7 to 19, more preferably 7 to 12). These groups may have a substituent within the range of exhibiting the effect of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly preferably a straight-chain, branched, or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12). , It is more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and still more preferably 3 to 12) which may have a substituent, and a cyclohexyl group that may have a substituent is more preferable do.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, 6-10 are more preferable), an alkenyl group (C2-24 are preferable, 2-12 are more preferable, 2-6 are more preferable), an arylalkyl group (C7-23 are preferable, 7-12 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), an arylalkenyl group (C 8 to 24 is preferable, 8 to 20 are more preferable, and 8 to 16 are more preferable), an alkoxyl group (C 1 to C 16 is preferable) 24 is preferable, 2 to 18 are more preferable, 3 to 12 are more preferable), aryloxy group (C6 to 22 are preferable, 6 to 18 are more preferable, 6 to 12 are still more preferable) , or an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Especially, a cycloalkyl group (C3-C24 is preferable, 3-18 are more preferable, and 3-12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent within the range showing the effect of the present invention.

It is preferable that the compound represented by formula (B1) is a compound represented by the following formula (B1-1) or the following formula (B1-2).

[Formula 38]

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 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 -12 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ are each independently 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), an alkenyl group (preferably 2 to 12 carbon atoms) and, more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group ( 7-23 carbon atoms are preferable, 7-19 are more preferable, and 7-11 are still more preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3-8 are more preferable), aryl group (C6-22 are preferable, 6-18 are more preferable, 6-12 are more preferable), arylalkyl group (C7-23 are preferable, 7-18 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), and an aryl group is preferable.

As for the compound represented by formula (B1-1), the compound represented by formula (B1-1a) is also preferable.

[Formula 39]

Rb ¹¹ and Rb ¹² have the same meaning as Rb ¹¹ and Rb ¹² in 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, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms and 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, and still more preferably 6 to 10), an arylalkyl group (7 to 23 carbon atoms) preferably, 7 to 19 are more preferable, and 7 to 11 are still 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, and even more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and 3 -8 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and among them, an aryl group is preferable.

[Formula 40]

(B3)

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a link chain connecting adjacent oxygen atoms and carbon atoms, and is a hydrocarbon having 3 or more atoms on the path of the link chain represents a flag. Further, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "linked chain" refers to linking these linking objects in the shortest (minimum number of atoms) among atomic chains on a path connecting between two atoms or groups of atoms to be linked. 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, the linked chain is composed of 4 carbon atoms, and the number of atoms on the path of the linked chain ( That is, the number of atoms constituting the linked chain, hereinafter also referred to as “linked chain length” or “linked chain length”) is 4.

[Formula 41]

It is preferable that the number of carbon atoms in L in the formula (B3) (including carbon atoms other than carbon atoms in the link chain) is 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. As for a lower limit, it is more preferable that it is 4 or more. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, the upper limit of the link chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less. In particular, the length of the linked chain of L is preferably 4 or 5, and most preferably 4. As a specific preferable compound of a base generator, the compound of Paragraph No. 0102 - 0168 of International Publication No. 2020/066416, and the compound of Paragraph No. 0143 - 0177 of International Publication No. 2018/038002 are also mentioned, for example. .

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1).

[Formula 42]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. It is preferable that it is 1 or more, and, as for the length of the linked chain of a linking group, it is more preferable that it is 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and still more preferably 5 or less. Linked chain length is the number of atoms present in the atomic arrangement that forms the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 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. (C1-24 is preferable, 1-12 are more preferable, and 1-10 are more preferable), and specifically, an aliphatic hydrocarbon group (C1-24 is preferable, 1-12 is more preferable, more preferably 1 to 10) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and aliphatic carbonization Hydrogen groups are preferred. As R ^N1 and R ^N2 , it is preferable to use an aliphatic hydrocarbon group because the basicity of the generated base is high. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, an aspect in which an aliphatic hydrocarbon group has an oxygen atom in a hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a straight-chain 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 alkyl group having an oxygen atom in the chain. The straight-chain or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12. The straight chain 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, an isopropyl group, Isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, etc. are mentioned.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, 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, and a cyclooctyl group.

The group relating to the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, still more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.

The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The alkyl group having an oxygen atom in its chain may be chain or cyclic, or may be straight or branched.

Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in formulations that place importance on adhesion when stacking with a layer of metal (for example, copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 and R ^N2 may be connected to each other to form a cyclic structure. In forming a cyclic structure, you may have an oxygen atom etc. in a chain|strand. Further, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic or condensed ring, but a monocyclic structure is preferable. As the cyclic structure formed, a 5- or 6-membered ring containing a nitrogen atom in formula (N1) is preferable, and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, and an imidazolidine ring. , A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. are mentioned, A pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring are mentioned preferably.

R ^C1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

As the protecting group, a protecting group decomposed by the action of an acid or a base is preferable, and a protecting group decomposed by an acid is preferably used.

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. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Examples of the chain-like alkyl group having an oxygen atom in the chain include, specifically, an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. 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, and a tetrahydropyranyl (THP) group.

The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and 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, a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or an oxygen atom in the chain A group related to a combination of a divalent aliphatic hydrocarbon group that may have a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group that 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, still more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, still more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and more preferably 7 to 10 desirable.

As the linking group L, specifically, a straight chain 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, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenyl A rene group, a cyclic alkenylene group, an arylene group, and an arylene alkylene group are preferable.

The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

The group relating to the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, still more preferably 4 to 6.

The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be straight or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 3. The number of C=C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2.

The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10.

The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11.

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 propanediyl group (especially 1 ,3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene A group (particularly a 1,2-phenylenemethylene group) and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following examples, but the present invention is not construed as being limited thereto.

[Formula 43]

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

As a specific preferable compound of an ionic base generator, Paragraph No. 0148 of International Publication No. 2018/038002 - the compound of 0163 are also mentioned, for example.

Although the following compounds are mentioned as a specific example of an ammonium salt, this invention is not limited to these.

[Formula 44]

Although the following compounds are mentioned as a specific example of an iminium salt, this invention is not limited to these.

[Formula 45]

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 relative 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 more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, or may be 4 parts by mass or less.

1 type or 2 or more types can be used for a base generator. When using 2 or more types, it is preferable that the total amount is the said range.

<Polymerizable compound>

It is preferable that the resin composition of this invention contains a polymeric compound.

As a polymeric compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical Crosslinking Agent]

It is preferable that the resin composition of this invention contains a radical crosslinking agent.

A radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include groups 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 a group containing the said ethylenically unsaturated bond, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and a (meth)acryloyl group is more preferable from a reactive viewpoint.

It is preferable that it is a compound which has one or more ethylenically unsaturated bonds, but, as for a radical crosslinking agent, it is more preferable that it is a compound which has two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

As the compound having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferable, compounds having 2 to 10 ethylenically unsaturated bonds are more preferable, and compounds having 2 to 6 this is more preferable

Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. .

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. As for the lower limit of the molecular weight of a radical crosslinking agent, 100 or more are preferable.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, preferably unsaturated These are esters of carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or a monofunctional or polyfunctional carboxylic acid Dehydration condensation reactants and the like are also suitably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, furthermore, a halo xeno group, a tosyloxy group, etc. Also suitable are substitution reactants of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers and the like instead of the above unsaturated carboxylic acids. As a specific example, Paragraph 0113 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0122 can be considered into consideration, and these content is integrated in this specification.

Moreover, the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanedioldi(meth)acrylate, trimethylolpropane tri(acryloyl Compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as oxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated compounds, Japan Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication Polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, epoxy acrylic which is a reaction product of epoxy resin and (meth)acrylic acid Polyfunctional acrylates and methacrylates, such as lates, and mixtures thereof are exemplified. Moreover, Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - the compound of 0257 are also suitable. Moreover, the polyfunctional (meth)acrylate obtained by making the compound which has a cyclic ether group, such as glycidyl (meth)acrylate, and an ethylenically unsaturated bond react with polyfunctional carboxylic acid, etc. are mentioned.

In addition, as preferred radical crosslinking agents other than those described above, those described in Japanese Unexamined Patent Publication No. 2010-160418, Japanese Unexamined Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc., have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. Hei 01-040337, and Japanese Patent Publication Hei 01-040336, and Japanese Unexamined Patent Publication Hei 02-025493 and the vinylphosphonic acid-based compounds described in No. Moreover, the compound containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, Journal of the Japan Adhesion Association vol. 20, no. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.

In addition to the above, the compound of Paragraph 0048 of Unexamined-Japanese-Patent No. 2015-034964 - 0051, and the compound of Paragraph 0087 of International Publication No. 2015/199219 - 0131 can also be used preferably, These content is integrated in this specification.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-062986, (meth)acrylated A compound can also be used as a radical crosslinking agent.

In addition, Paragraph 0104 of Unexamined-Japanese-Patent No. 2015-187211 - the compound of 0131 can also be used as a radical crosslinking agent, These content is integrated in this specification.

As a radical crosslinking agent, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) , A-TMMT: Shin Nakamura Chemical Industry Co., Ltd. product), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa (meth) ) Acrylates (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and their (meth)acryloyl groups are ethylene glycol residues or propylene glycol residues A structure bonded via is preferable. These oligomeric types can also be used.

As a commercially available product of the radical crosslinking agent, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, 231, 239, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane Oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo), DPHA- 40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Nichiyu ( Note) and the like.

Examples of the radical crosslinking agent include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765. Retane acrylates, ethylene oxide systems described in Japanese Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, Japanese Publication No. 62-039418 Urethane compounds having a skeleton are also suitable. In addition, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. Hei 01-105238 can be used. can also be used

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group do. Particularly preferably, in a radical crosslinking agent obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. am. As a commercial item, M-510, M-520 etc. are mentioned, for example as a Toagosei Co., Ltd. product polybasic acid modified acrylic oligomer.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. When the acid value of the radical crosslinking agent is in the above range, the handleability in production is excellent, and furthermore, the developability is excellent. Moreover, polymerizability is good. The said acid value is measured based on description of JISK0070:1992.

For the resin composition, it is preferable to use a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability.

As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, 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 Rate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylic acid of bisphenol A Rate, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified Diacrylates, isocyanuric acid-modified dimethacrylates, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. These can mix and use 2 or more types as needed.

In addition, for example, PEG200 diacrylate is polyethylene glycol diacrylate, and means that the formula of a polyethylene glycol chain is about 200.

In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of curvature suppression by controlling the modulus of elasticity of the pattern (cured product). As a monofunctional radical crosslinking agent, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl Ether and the like are preferably used. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

In addition, allyl compounds, such as a diallyl phthalate and triallyl trimellitate, are mentioned as a bifunctional or more than bifunctional radical crosslinking agent.

When containing a radical crosslinking agent, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solids of the resin composition of this invention. As for a lower limit, 5 mass % or more is more preferable. As for an upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, but may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

[Other crosslinking agents]

It is also preferable that the resin composition of this invention contains another crosslinking agent different from the radical crosslinking agent mentioned above.

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and a covalent bond between the above-mentioned photoacid generator or photobase generator and other compounds in the composition or a reaction product thereof by photosensitization of the photoacid generator. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction to form a group in the molecule that promotes the reaction of forming a covalent bond with other compounds or reaction products thereof in the composition by the action of an acid or base. A compound having a plurality of them is preferable.

The acid is preferably an acid generated from a photoacid generator in the exposure step.

As another crosslinking 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 at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is a nitrogen atom A compound having a structure directly bonded to is more preferred.

As another crosslinking agent, for example, formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methyl Compounds having a structure substituted with an all group or an alkoxymethyl group are exemplified. The manufacturing method of these compounds is not specifically limited, Any compound having the same structure as the compound manufactured by the said method is sufficient. Moreover, the oligomer formed by self condensation of the methylol groups of these compounds may be sufficient.

As the amino group-containing compound, a crosslinking agent using melamine is a melamine crosslinking agent, glycoluril, a crosslinking agent using urea or an alkylene urea is a urea crosslinking agent, a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent, benzoguanamine A crosslinking agent using is called a benzoguanamine-based crosslinking 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 crosslinking agent and a melamine-based crosslinking agent, and from the group consisting of a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described later. It is more preferable to include at least one selected compound.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine It can be mentioned as a structural example.

The alkoxymethyl group or acyloxymethyl group of the compound has preferably 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 of the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.

[Formula 46]

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 acyloxymethyl group is directly substituted with an aromatic group include compounds of the following general formula.

[Formula 47]

In the formula, X represents a single bond or a 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, an aralkyl group, or an acid A group that is decomposed by the action and generates 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 are each independently a hydrogen atom or a carbon number) represents an alkyl group of 1 to 4, and R ⁵ represents a group that is eliminated by the action of an acid.)).

R ₁₀₅ Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, and 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 decomposed by the action of an acid to generate an alkali-soluble group, a group desorbed ^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 bonded to each other to form a ring.

As said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C5 alkyl group is more preferable.

The alkyl group may be linear or branched.

As said cycloalkyl group, a C3-C12 cycloalkyl group is preferable, and a C3-C8 cycloalkyl group is more preferable.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

It is preferable that the said aryl group is a C6-C30 aromatic hydrocarbon group, and it is more preferable that it is a phenyl group.

As said aralkyl group, a C7-C20 aralkyl group is preferable, and a C7-C16 aralkyl group is more preferable.

The 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-described 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.

Moreover, these groups may further have a well-known substituent within the range in which the effect of this invention is acquired.

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 tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups and the like. More preferably, it is a tertiary alkyl ester group and an acetal ester group.

As a compound which has an alkoxymethyl group, the following structures are specifically mentioned. Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds has been changed to an acyloxymethyl group. Although the following compounds are mentioned as a compound which has an alkoxymethyl group or acyloxymethyl in a molecule|numerator, It is not limited to these.

[Formula 48]

[Formula 49]

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.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of the urea-based crosslinking agent include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxy Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril , trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated Glycoluril-based crosslinking agents such as glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril ; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea, monohydroxymethylated ethylene urea, dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea Ethylene urea crosslinking agent, monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, etc. Propylene urea-based crosslinking agents such as monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea, 1,3-di(methoxymethyl)-4,5 -Dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc. are mentioned.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, and monomethoxymethylated benzoguanamine. Namine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, Tetraethoxymethylated Benzoguanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine, Monobutoxymethylated Benzoguanamine, Dibu Toxymethylation benzoguanamine, tributoxymethylation benzoguanamine, tetrabutoxymethylation benzoguanamine, etc. are mentioned.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring). are also suitably used.

Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, Hydroxymethylbenzoic acid Hydroxymethylphenyl, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl) Dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzoic acid methoxymethylphenyl, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl) Biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(tri Fluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3 ', 5,5'-tetrakis (methoxymethyl) -1,1'-biphenyl-4 , 4'-diol, etc. are mentioned.

Commercially available products may be used as other crosslinking agents, and suitable commercially available products include 46DMOC, 46DMOEP (above, manufactured by Asahi Yukizai Kogyo Co., Ltd.), 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 (above, made by Honshu Kagaku Kogyo), Nikarak ( (registered trademark, hereinafter the same) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (above, manufactured by Sanwa Chemical Co., Ltd.), etc. there is.

Moreover, it is also preferable that the resin composition of this invention contains at least 1 sort(s) of compound selected from the group which consists of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

-Epoxy compound (compound having an epoxy group)-

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or lower and no dehydration reaction resulting from the crosslinking occurs, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in low-temperature hardening of the resin composition of this invention and suppression of curvature.

It is preferable that the epoxy compound contains a polyethylene oxide group. Thereby, the modulus of elasticity is lowered and the warpage can be suppressed. A polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2-15.

As an example of an epoxy compound, it is bisphenol-A 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 alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as diglycidyl ether and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (above product names, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-20E, Rica Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, New Japan Rica Co., Ltd.), EP- 4003S, EP-4000S, EP-4088S, EP-3950S (above product names, manufactured by 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 (above product names, 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 (above brand name, Nippon Kayaku Co., Ltd. product), etc. are mentioned. Moreover, the following compounds are also used suitably.

[Formula 50]

In the formula, n is an integer of 1 to 5, m is an integer of 1 to 20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.

-Oxetane compound (compound having an oxetanyl group)-

As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 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 (eg, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be suitably used, and these may be used alone or in combination of two or more.

-Benzoxazine compound (compound having a benzoxazolyl group)-

The benzoxazine compound is preferable in that it does not generate degassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and suppresses occurrence of warpage by reducing heat shrinkage.

Preferable examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolak-type dihydrobenzene. An oxazine compound is mentioned. These may be used independently or may mix 2 or more types.

The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and preferably 1.0 to 15% by mass, based on the total solid content of the resin composition of the present invention. It is especially preferable that it is 10 mass %. Another crosslinking agent may contain only 1 type, and may contain 2 or more types. When 2 or more types of other crosslinking agents are contained, it is preferable that the sum total is the said range.

<Metal Adhesion Improver>

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, and the like. As the metal adhesion improving agent, a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, β- A keto ester compound, an amino compound, etc. are mentioned.

[Silane coupling agent]

As a silane coupling agent, the compound of Paragraph 0167 of International Publication No. 2015/199219, the compound of Paragraph 0062 of Unexamined-Japanese-Patent No. 2014-191002 - the compound of 0073, Paragraph 0063 of International Publication No. 2011/080992, for example The compound described in ~ 0071, the compound described in paragraphs 0060 to 0061 of Japanese Laid-open Patent Publication No. 2014-191252, the compound described in paragraphs 0045 to 0052 of Japanese Patent Laid-Open No. 2014-041264, and the paragraph 0055 of International Publication No. 2014/097594 A compound and Paragraph 0067 of Unexamined-Japanese-Patent No. 2018-173573 - the compound of 0078 are mentioned, These content is integrated in this specification. Moreover, it is also preferable to use 2 or more types of silane coupling agents different as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Me represents a methyl group and Et represents an ethyl group.

[Formula 51]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl -3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mer Captopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic acid anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based adhesive aid]

Examples of aluminum-based adhesive aids include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Moreover, as other metal adhesion improving agents, the compound described in Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide-type compound of Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 can also be used, These content is incorporated herein.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By using the above lower limit or more, the adhesion between the pattern and the metal layer becomes good, and by using the above upper limit or less, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Migration inhibitor>

It is preferable that the resin composition of this invention further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

The migration inhibitor is not particularly limited, but is a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring) compounds having thioureas and sulfanyl groups , hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole-based compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; Tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion trapping agent that traps negative ions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP-A-2013-015701, the compound described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compound described in paragraph 0052 of JP-A-2011-059656, The compound of Paragraph 0114 of Unexamined-Japanese-Patent No. 2012-194520, 0116, and 0118, the compound of Paragraph 0166 of International Publication No. 2015/199219, etc. can be used, These content is integrated in this specification.

Specific examples of the migration inhibitor include the following compounds.

[Formula 52]

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, and more preferably 0.05 to 2.0% by mass, based on the total solid content of the resin composition of the present invention. It is more preferable that it is 0.1-1.0 mass %.

One type of migration inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of migration inhibitors, it is preferable that the sum total is the said range.

<Polymerization inhibitor>

It is preferable that the resin composition of this invention 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 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, and p-tert-butylcateta Col, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine , ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycoletherdiamine 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-sulfopropylamino)phenol, N-nitro Bovine-N-(1-naphthyl)hydroxyamineammonium 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-picrylhyd Razil, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are suitably used. used Moreover, the polymerization inhibitor of Unexamined-Japanese-Patent No. 2015-127817, Paragraph 0060, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used, The content is integrated in this specification.

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, and more preferably 0.02 to 15% by mass with respect to the total solid content of the resin composition of the present invention. And, it is more preferable that it is 0.05 to 10% by mass.

1 type of polymerization inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of polymerization inhibitors, it is preferable that the sum total is the said range.

<Other additives>

The resin composition of the present invention may contain, as necessary, various additives such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, Phenol-based compounds, other high molecular compounds, plasticizers, and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.) can be blended. By appropriately containing these components, properties such as membrane properties can be adjusted. These components are, for example, described in paragraph No. 0183 of Japanese Laid-open Patent Publication No. 2012-003225 (paragraph No. 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph No. 2008-250074 Reference can be made to descriptions of 0101 to 0104 and 0107 to 0109, the contents of which are incorporated herein by reference. When blending these additives, the total compounding amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactants〕

As surfactant, various surfactants, such as a fluorochemical surfactant, a silicone type surfactant, and a hydrocarbon type surfactant, can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, in the case of forming a film 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 lowered, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is reduced. It improves. For this reason, it is possible to more suitably form a film having a uniform thickness with little thickness unevenness.

Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F143. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Fluorad FC430, copper FC431, copper FC171, Novec FC4430, copper FC4432 (above, manufactured by 3M Japan Co., Ltd.), West Front S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 ( As mentioned above, Asahi Glass Co., Ltd. product), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned. The compound described in Paragraph 0015 of Unexamined-Japanese-Patent No. 2015-117327 - 0158, and Paragraph 0117 of Unexamined-Japanese-Patent No. 2011-132503 - the compound of 0132 can also be used for a fluorochemical surfactant, The content of these is integrated in this specification. . A block polymer can also be used as a fluorochemical surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example, These content is integrated in this specification.

The fluorine-based surfactant is a (meth)acrylate compound having 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group). ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 53]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

As the fluorochemical surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain may be used as the fluorochemical surfactant. As a specific example, Paragraph 0050 of Unexamined-Japanese-Patent No. 2010-164965 - 0090 and Paragraph 0289 - the compound of 0295 are mentioned, This content is integrated in this specification. Moreover, as a commercial item, DIC Corporation Megafac RS-101, RS-102, RS-718K etc. are mentioned, for example.

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 the uniformity of the thickness of the coating film and liquid saving, and has good solubility in the composition.

As the silicone surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) product), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Examples of hydrocarbon surfactants include Pionin A-76, New Cargen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, 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 (above, Takemoto Yushi Co., Ltd.), etc. are mentioned.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , sorbitan fatty acid ester, etc. are exemplified. As commercially available products, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 ( Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (made by Wako Junyaku Kogyo Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Yushi Takemoto) Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (Nisshin Chemical Co., Ltd. product), etc. are mentioned.

As the cationic surfactant, specifically, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, no. 77, no. 90, no. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

Specifically as anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), Sandet BL (made by Sanyo Kasei Co., Ltd.), etc. are mentioned.

Surfactant may use only 1 type, and may combine 2 or more types.

The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher Fatty Acid Derivatives]

To the resin composition of the present invention, in order to prevent inhibition of polymerization due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added and unevenly distributed on the surface of the resin composition of the present invention during drying after application. .

Moreover, as a higher fatty acid derivative, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is integrated in this specification.

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. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

[Inorganic Particles]

The resin composition of the present invention may also contain inorganic fine particles. Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass and the like.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

The average particle diameter of the fine particles is a primary particle diameter and is also a volume average particle diameter. 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.).

When the above measurement is difficult, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Ultraviolet rays absorber]

The composition of the present invention may contain a ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type, and triazine type can be used.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydride Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4-octoxy benzophenone, etc. are mentioned. In addition, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 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 azoles, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and the like. Further, as an example of the triazine-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. Mono (hydroxyphenyl) triazine compounds of; 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 bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 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]- and tris(hydroxyphenyl)triazine compounds such as 1,3,5-triazine.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.01 mass % or more and 0.1 mass % or less.

[organic titanium compound]

The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelate compound: Especially, the titanium chelate compound which has 2 or more alkoxy groups is more preferable at the point from which the storage stability of a resin composition is favorable and a favorable curing pattern is obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-phen theindionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2] ,2-(allyloxymethyl)butoxide}] and the like.

III) titanocene compounds: eg pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxy titanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate and the like.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the viewpoint that the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, which exhibits better chemical resistance. preferred in In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro Rho-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, elongation characteristics of the film after curing and adhesion to a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. As the phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) oxy]ethyl]amine, phosphorous acid ethylbis(2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of an antioxidant, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, for example, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, made by ADEKA Co., Ltd.), etc. are mentioned. Moreover, the antioxidant can also use the compound of Paragraph No. 0023 of Unexamined-Japanese-Patent No. 6268967 - 0048, The content of this is integrated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As the latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is released by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. As a latent antioxidant, the compound of international publication 2014/021023, international publication 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned, The content of this is integrated in this specification. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned.

Examples of preferable antioxidants include compounds represented by 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and Formula (3).

[Formula 54]

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 group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). . R ⁷ represents a monovalent 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 from 1 to 4;

The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust-preventive effect on the metal material.

Since it can act simultaneously on the resin and the metal material, k is more preferably an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, what combined them, etc. are mentioned, You may have a substituent further. Among these, from the viewpoint of solubility in a developing solution and metal adhesion, those having an alkyl ether group and -NH- are preferable, and -NH- is more preferable from the viewpoint of interaction with resin and metal adhesion due to metal complexation. .

Although the following are mentioned as an example of the compound represented by General formula (3), It is not limited to the following structure.

[Formula 55]

[Formula 56]

[Formula 57]

[Formula 58]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 parts by mass or more, the effect of improving the elongation properties and adhesion to metal materials is easily obtained even in a high-temperature, high-humidity environment, and by setting it to 10 parts by mass or less, for example, by interaction with the photosensitive agent, The sensitivity of the composition is improved. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that those total amounts become the said range.

[anti-agglomeration agent]

The resin composition of this embodiment may contain an aggregation inhibitor as needed. As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

In this invention, an aggregation inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain an aggregation inhibitor, but when it is included, the content of the aggregation inhibitor is preferably 0.01% by mass or more and 10% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.02 mass % or more and 5 mass % or less.

[phenolic compound]

The resin composition of this embodiment may contain a phenolic compound as needed. As the phenolic compound, 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, Methylenetris-FR-CR, BisRS-26X (above, product name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F (above, brand name, Asahi Yukizai Kogyo Co., Ltd. product), etc. are mentioned.

In this invention, a phenol type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain a phenolic compound, but when it is included, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention and more preferably 0.02% by mass or more and 20% by mass or less.

[Other high molecular compounds]

Examples of other high molecular compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins, copolymers thereof, and the like. The other high molecular compound may be a modified body into which a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group has been introduced.

In the present invention, the other high molecular compounds may be used singly or in combination of two or more.

The composition of the present invention may or may not contain other high molecular compounds, but in the case where they are included, the content of the other high molecular compounds is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention. and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of Resin Composition>

The viscosity of the resin composition of the present invention can be adjusted by 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 are preferred, 2,000 mm ² /s to 10,000 mm ² /s are more preferred, and 3,000 mm ² /s to 8,000 ^{mm 2} /s are preferred. more preferable If it is the said range, it becomes easy to obtain a coating film with high uniformity. At 1,000 mm ² /s or less, it is difficult to apply the film to a film thickness required as, for example, an insulating film for rewiring, and at 12,000 mm ² /s or more, the coated surface shape may deteriorate.

<Restrictions on Materials Contained in Resin Composition>

The moisture 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 still more preferably less than 1.0% by mass. At 2.0% or more, there is a possibility that the storage stability of the resin composition is impaired.

As a method of maintaining the content of water, adjustment of humidity in storage conditions, reduction of the porosity of the container at the time of storage, etc. are mentioned.

From an insulating viewpoint, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, it is preferable that the sum of these metals is within the above range.

In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention, or a raw material constituting the resin composition of the present invention For example, a method of performing filter filtration on the substrate, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible is exemplified.

In the resin composition of the present invention, considering the use as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. more preferable Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively is within the above range.

As a method of adjusting the content of halogen atoms, ion exchange treatment or the like is preferably used.

A conventionally well-known container can be used as a container for the resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multi-layered bottle in which the inner wall of the container is made of 6 types of 6-layer resin, and a bottle in which 6 types of resin are used in a 7-layer structure It is also preferable to use As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<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 formed by curing the resin composition of the present invention.

Curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and more preferably in the range of 170°C to 350°C. What is within the range is particularly preferred. The shape of the cured product of the resin composition is not particularly limited, and may be selected according to the application, such as a film shape, a rod shape, a spherical shape, or a pellet shape. In this invention, it is preferable that this hardened|cured material is film-like. In addition, by pattern processing of the resin composition, according to the application, such as formation of a protective film on the wall surface, formation of via holes for conduction, adjustment of impedance, capacitance or internal stress, imparting a heat dissipation function, The shape of this cured product can also be selected. It is preferable that the film thickness of this hardened|cured material (film|membrane consisting of hardened|cured material) is 0.5 micrometer or more and 150 micrometer or less.

The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated from the following formula.

Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

<Characteristics of cured product of resin composition>

The imidation reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If less than 70%, there is a possibility that the mechanical properties of the cured product are 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, and 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 still more preferably 230°C or higher.

(developer)

The developer of the present invention is a developer used in the method for producing a cured product of the present invention.

The developing solution of the present invention has the same meaning as the developing solution described in the developing step of the production method of the cured product of the present invention described above, and the preferred embodiments are also the same.

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are based on mass unless otherwise specified.

<Synthesis of Acetal Forms A-1 and A-2>

[Formula 59]

In a one-necked flask, 34.90 g (260 mmol) of 2-phenylpropionaldehyde (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 59.60 g (572 mmol) of ethylene glycol monopropyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.6 g (2.6 mmol) of (±)-10-camphorsulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 30 g of magnesium sulfate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to obtain a reaction solution. After stirring the obtained reaction solution at 25 degreeC for 30 minutes, it heated up to 50 degreeC and stirred for 24 hours. The solution after stirring was cooled to 25°C, and after adding 1.32 g (13 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), it was dissolved in 500 mL of ethyl acetate and transferred to a separatory funnel. After washing the ethyl acetate solution in the separatory funnel three times with 200 mL of saturated sodium bicarbonate water, the solvent was removed with an evaporator to obtain 72 g of acetal body A-1.

Acetal body A-2 was synthesized in the same manner.

[Formula 60]

<Synthesis of chloroforms B-1 and B-2>

To a one-necked flask, 72 g of A-1 synthesized above and 19.1 g (243 mmol) of acetyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to obtain a reaction solution. After the obtained reaction solution was stirred at 25°C for 1 hour, the temperature was raised to 45°C and stirred for 4 hours to obtain 91 g of chloroform B-1.

[Formula 61]

Chloroform B-2 was synthesized in the same manner.

[Formula 62]

<Synthesis Example: Synthesis of Polymer P-1>

After adding 31.02 g (100 mmol) of 4,4'-oxydiphthalic dianhydride and 145 g of N-methylpyrrolidone (NMP) to a flask, while stirring at 25°C, 4,4'-diaminodiphenyl 18.02 g (90 mmol) of ether 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, followed by 2-methoxyethoxymethyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 24.91 g (200 mmol) was added dropwise over 1 hour, and stirred at -10 to -5°C for 1 hour. After adding the obtained solution after stirring to 5 L of methanol, it stirred for 30 minutes. After the solution after stirring was left still for 30 minutes, the supernatant liquid was discarded to obtain a solid substance. After dissolving this solid matter in 300 mL of tetrahydrofuran, it was added to hexane 5L, stirred for 30 minutes, then filtered and dried to obtain 56 g of polymer P-1.

<Synthesis Example: Synthesis of Polymer P-2>

After adding 9.64 g (130 mmol) of t-butyl alcohol and 30 mL of tetrahydrofuran to the flask and cooling to -10°C, 43.7 g of n-butyllithium (20% by mass cyclohexane solution) was added dropwise, and TB- got 1

In a flask different from the above, 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride was suspended in 100 mL of diglyme, and 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were successively added, Furthermore, the above TB-1 was added dropwise over 1 hour using a dropping funnel, and then stirred at a temperature of 25°C for 5 hours. After cooling the obtained mixture 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, after heating the mixture containing the white precipitate to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a solution. Subsequently, a solution obtained 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 solution. After adding 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene to the obtained liquid mixture, it stirred for 2 hours. Next, after adding the liquid mixture after stirring to 4 liters of water to precipitate the polyimide precursor resin, the mixture was stirred at a speed of 500 rpm for 15 minutes. After obtaining by filtering polyimide precursor resin, the obtained polyimide precursor resin was added to 4 liters of water, it stirred again for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain 33 g of P-2.

<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.

<Synthesis Example: Synthesis of Polymer P-4>

Polymer P-4 was synthesized in the same manner as in P-1, except that an equimolar amount of B-2 was used instead of 2-methoxyethoxymethyl chloride.

<Synthesis Example: Synthesis of Polymer P-5>

After adding 29.42 g (100 mmol) of 4,4'-biphthalic anhydride and 145 g of N-methylpyrrolidone (NMP) to a flask, 4,4'-diaminodiphenyl ether 18.02 was stirred at 25°C. g (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 dropwise over 1 hour. and stirred for 1 hour at -10 to -5°C. After adding the obtained solution after stirring to 5 L of methanol, it stirred for 30 minutes. After the solution after stirring was left still for 30 minutes, the supernatant liquid was discarded to obtain a solid substance. After dissolving this solid matter in 300 mL of tetrahydrofuran, it was added to hexane 5L, stirred for 30 minutes, then filtered and dried to obtain 52 g of polymer P-5.

<Synthesis Example: Synthesis of Polymer P-6>

Polymer P-6 was synthesized in the same manner as in P-1, except that the amount of 4,4'-diaminodiphenyl ether added was changed to 16.0 g (80 mmol).

<Examples and Comparative Examples>

In each Example, each resin composition was obtained by mixing the components described in the table below, respectively. Moreover, in the comparative example, the components described in the table below were mixed to obtain a composition for comparison.

Specifically, the content of the components described in the table was set to the amount described in the column of "parts by mass" in the table. In addition, in each composition, the content of the solvent was such that the solid content concentration of the composition became the value (% by mass) described in the table.

The obtained resin composition and comparative composition were subjected to pressure filtration through a filter made of polytetrafluoroethylene having a filter pore size of 0.8 µm.

In addition, in the table|surface, description of "-" shows that the composition does not contain the component concerned.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

The detail of each component described in the table|surface is as follows.

〔profit〕

P-1 to P-6: P-1 to P-6 synthesized above

[Crosslinking agent (polymerizable compound)]

B-1 to B-4: Compounds with the following structures

[Formula 63]

[mine generator]

C-1 to C-4: Compounds with the following structures

[Formula 64]

[Photoinitiator]

・I-1: Irgacure OXE-01 (manufactured by BASF)

[Silane coupling agent]

D-1: 3-glycidoxypropylmethyldimethoxysilane

D-2: a compound having the following structure

[Formula 65]

[migration inhibitor]

E-1: tetrazole

[Additive (acid trapping agent)]

F-1: tridodecylamine

F-2: triphenylimidazole

F-3: DBU (diazabicycloundecene)

〔solvent〕

GBL: γ-butyrolactone

DMSO: dimethyl sulfoxide

In the table, the description in the column of “ratio” indicates the content (% by mass) of each solvent relative to the total mass of the solvent.

(evaluation)

<Resolution Evaluation>

In each Example and Comparative Example, a resin composition or a comparative composition was applied on a silicon substrate by a spin coating method to form a coating film. Next, using a hot plate, a heat treatment was performed for 300 seconds at the temperature described in "PB temperature (°C)" in the table to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after rinsing became the value described in the column of "film thickness after modification (μm)" in the table.

Next, the resin composition layer was exposed using an i-line filter with a broadband exposure machine (manufactured by Ushio Electric Co., Ltd.: UX-1000SN-EH01). The exposure amount was 400 mJ/cm ² . As the photomask, a ceramic plate test chart (No. 1, negative type, manufactured by Ceramic Ceramics Insatsu) was used.

After exposure, the resin composition layer was heated for 300 minutes using a hot plate at the temperature described in the column of "PEB temperature (°C)" in the table. In addition, in the example described with "-" in the column of "PEB temperature (°C)", heating was not performed.

After the above heating, development was performed at 23° C. for 60 seconds using the developer described in the column of “developer” in the table to form a pattern.

After the 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 were described in the column of "Resolution" in the table.

-Evaluation standard-

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 exceeded 20 μm.

<Evaluation of dimensional stability of the first layer during multi-layer lamination>

[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 spin coating to form a coating film. Then, using a hot plate, a heat treatment was performed for 300 seconds at the temperature described in "PB temperature (°C)" in the table 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 using a stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.) using a photomask having a 1:1 line-and-space pattern with a line width of 20 μm. The exposure amount was 400 mJ/cm ² .

After exposure, the resin composition layer was heated for 5 minutes using a hot plate at the temperature described in the column of "PEB temperature (°C)" in the table. In addition, in the example described with "-" in the column of "PEB temperature (°C)", heating was not performed.

After the above heating, development was performed at 23° C. for 60 seconds using the developer described in the column of “developer” in the table to form a pattern.

After the development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).

The 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 first-layer pattern.

In the example described as "N ₂ Oven" in the column of "Heating Means", heating was performed using CLH-21 manufactured by Koyo.

In addition, in the example described as "IR oven" in the column of "heating means", heating was performed using RTP-6 manufactured by Advance Reco.

[Formation of the second layer]

In each Example and Comparative Example, the same resin composition or comparative composition was applied again on the first layer of the cured product by spin coating to form a coating film. Next, using a hot plate, a heat treatment was performed for 300 seconds at the temperature described in "PB temperature (°C)" in the table 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 using a stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.) using a photomask having a 1:1 line-and-space pattern with a line width of 20 μm. The exposed portion through the 1:1 line and space pattern was set so that the line portion and the space portion were orthogonal to the exposed portion in the first layer. The exposure amount was 400 mJ/cm ² .

After exposure, the resin composition layer was heated for 5 minutes using a hot plate at the temperature described in the column of "PEB temperature (°C)" in the table. In addition, in the example described with "-" in the column of "PEB temperature (°C)", heating was not performed.

After the above heating, development was performed at 23° C. for 60 seconds using the developer described in the column of “developer” in the table to form a pattern.

After the development, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate).

The 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 section of "Heating Means", heating was performed using CLH-21 manufactured by Koyo to obtain a second-layer cured product.

Moreover, in the example described as "IR oven" in the column of "heating means", heating was performed using RTP-6 manufactured by Advanced Reco, to obtain a second layer cured product.

〔evaluation〕

The line width (line width A) of the first-layer cured product immediately after formation of the first-layer cured product (before formation of the coating film in the second-layer formation), and the first-layer cured product immediately after formation of the second-layer cured product The line width (line width B) was measured, and the dimensional variation (%) was calculated according to the following formula. Based on the value of the dimensional variation, the dimensional stability of the first layer was evaluated according to the following evaluation criteria. The evaluation results were described in the column of "Evaluation of dimensional stability of the first layer during multilayer lamination".

Dimension variation (%)=|line width A-line width B|/line width A×100

-Evaluation standard-

A: The dimensional variation (%) was 5% or less.

B: The dimensional variation (%) exceeded 5%.

<Evaluation of second layer resolution when multilayer stacking>

A first-layer cured product and a second-layer cured product were produced by the same method as the first-layer dimensional stability evaluation at the time of multilayer lamination.

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 during multilayer lamination" in the table.

-Evaluation standard-

A: The taper angle, which is an angle formed between the surface of the substrate and the side surface of the pattern, was 80° or more and less than 90°, and peeling of the pattern was not observed.

B: The taper angle was less than 80°, the cross-sectional shape of the pattern was a reverse tapered shape with a taper angle exceeding 90°, or the cross-sectional shape of the pattern was constricted, but peeling of the pattern was not observed.

C: Peeling of the pattern was confirmed.

In the method for producing the cured product according to Comparative Example 1, the polyimide precursor does not have a group generating a reaction in which 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 poor.

<Example 101>

The resin composition used in Example 1 was applied in a layer form to the surface of a copper foil layer of a resin substrate having a copper foil layer formed thereon by a spin coating method, and dried at 100°C for 300 seconds. Film thickness was made into the film thickness from which the film thickness of the hardened|cured material obtained becomes 5 micrometers. After that, it was exposed using a stepper (manufactured by Nikon Co., Ltd., NSR1505i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it heated at 120 degreeC for 300 second. After the 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.

Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10°C/min, and after reaching 230°C, the layer was cured while holding for 120 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing semiconductor devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (14)

A film formation step of forming a film by applying a resin composition containing a resin, a compound that generates an acid by irradiation with actinic rays or radiation, and a solvent on a substrate;
An exposure step of selectively exposing the film to light;
A developing step of developing the film after exposure using a developer to form a pattern, and
A denaturation step of denaturing the pattern;
The resin is a polyimide precursor,
The resin has a group that generates a reaction in which polarity is increased by the action of an acid,
The content of the organic solvent relative to the total mass of the developer is 80% by mass or more,
The method for producing a cured product in which the solubility of the pattern in the solvent contained in the resin composition is reduced by the modification. The method of claim 1,
The manufacturing method of the hardened|cured material whose film thickness of the hardened|cured material obtained is 5 micrometers or more. According to claim 1 or claim 2,
The manufacturing method of the hardened|cured material in which the said resin contains the repeating unit represented by following formula (1).
[Formula 1]

In the formula (1), R ¹ represents a tetravalent organic group; A plurality of R ¹ may be the same as or different from each other; R ² represents a divalent organic group; A plurality of R ² may be the same as or different from each other; R ³ each independently represents a hydrogen atom or an organic group. The method of claim 3,
The method for producing a cured product, wherein the repeating unit represented by the formula (1) has a group generating a reaction in which polarity is increased by the action of the acid. The method according to any one of claims 1 to 4,
The method for producing a cured product, wherein the resin composition further comprises a scattering agent. The method according to any one of claims 1 to 5,
The method for producing a cured product, wherein the developer contains 80% by mass or more of an organic solvent having a hydrogen bond term dH value of 8 or less in the Hansen solubility parameter. The method according to any one of claims 1 to 6,
A method for producing a cured product, wherein the group generating a reaction in which 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).
[Formula 2]

In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * indicates another structure indicates a binding site with;
In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, and at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * is a bond with another structure. indicates the area. According to any one of claims 1 to 7,
The method for producing a cured product in which the pattern is heated in the modification step. The method according to any one of claims 1 to 8,
The method for producing a cured product, further comprising a step of heating the film after the exposure step and before the developing step. A method for producing a laminate comprising repeating the method for producing a cured product according to any one of claims 1 to 9 a plurality of times. The method of claim 10,
The manufacturing method of the laminated body which further includes the metal layer formation process of forming a metal layer on the layer which consists of hardened|cured material between the manufacturing method of a hardened|cured material performed multiple times. The manufacturing method of the electronic device which includes the manufacturing method of the hardened|cured material in any one of Claims 1-9, or the manufacturing method of the laminated body of Claim 10 or Claim 11 as a process. The resin composition used for the manufacturing method of the hardened|cured material in any one of Claims 1-9. A developing solution used in the method for producing a cured product according to any one of claims 1 to 9.