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CN115038755A - Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device Download PDF

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Publication number
CN115038755A
CN115038755A CN202180012209.8A CN202180012209A CN115038755A CN 115038755 A CN115038755 A CN 115038755A CN 202180012209 A CN202180012209 A CN 202180012209A CN 115038755 A CN115038755 A CN 115038755A
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CN
China
Prior art keywords
group
ring
resin composition
curable resin
compound
Prior art date
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Pending
Application number
CN202180012209.8A
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Chinese (zh)
Inventor
高岛美沙树
山崎健太
村山哲
井上和臣
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN115038755A publication Critical patent/CN115038755A/en
Pending legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • H01L23/53295—Stacked insulating layers

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  • Polymers & Plastics (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The present invention provides a curable resin composition comprising at least one resin selected from the group consisting of a polyimide, a polyimide precursor, a polybenzoxazole and a polybenzoxazole precursor, and at least two solvents, a resin film obtained by applying the curable resin composition to a substrate, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.

Description

Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device
Technical Field
The present invention relates to a curable resin composition, a resin film, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
Background
Polyimide or polybenzoxazole has excellent heat resistance, insulation properties, and the like, and is therefore suitable for various applications. The use is not particularly limited, and examples of the use include use as a material for an insulating film or a sealing material, or use as a protective film, when a semiconductor device for actual mounting is used. Further, the film is also used as a base film (base film) or a cover film (cover film) of a flexible substrate.
For example, in the above-mentioned use, the polyimide or polybenzoxazole is used as at least one resin selected from the group consisting of a polyimide, a polyimide precursor, a polybenzoxazole and a polybenzoxazole precursor.
The curable resin composition can be applied to a substrate to form a resin film, for example, by coating, and then subjected to exposure, development, heating, and the like as necessary, thereby forming a cured film on the substrate.
The polyimide precursor and the polybenzoxazole precursor are cyclized by, for example, heating, and become polyimide and polybenzoxazole, respectively, in the cured film.
Since the curable resin composition can be applied by a known coating method or the like, it can be said that the curable resin composition has excellent production flexibility, and for example, the curable resin composition to be applied has a high degree of freedom in design such as shape, size, and application position when applied. In addition to the high performance of polyimide, polybenzoxazole, and the like, the industrial application and development of the curable resin composition are expected from the viewpoint of excellent suitability for such production.
For example, patent document 1 describes a composition containing: the solvent composition comprises a polyimide precursor, polyimide, at least one of a polybenzoxazole precursor and a polybenzoxazole resin, a crosslinking agent, a 1 st solvent which is obtained by dissolving more than 5 mass% of the resin at 25 ℃ and is selected from alcohols, esters, ketones, ethers, sulfur-containing compounds, carbonates and ureas, and a 2 nd solvent which has a solubility parameter distance of 3.0-11.0 from the 1 st solvent.
Patent document 2 describes a resin composition containing (a) a polyimide precursor or a polybenzoxazole precursor, and at least one polar solvent selected from a compound represented by a specific general formula (1), a compound represented by a specific general formula (2), and a compound containing a sulfur atom, wherein the content of N-methyl-2-pyrrolidone (NMP) in the resin composition is 0.1 mass% or less.
Prior art documents
Patent document
Patent document 1: international publication No. 2017/038664
Patent document 2: international publication No. 2014/115233
Disclosure of Invention
Technical problem to be solved by the invention
Among curable resin compositions, it is desired to provide a curable resin composition which is excellent in film thickness uniformity of a resin film obtained even in the case of a curable resin composition after long-term storage at low temperature.
An object of the present invention is to provide a curable resin composition which has excellent film thickness uniformity of an obtained resin film even when stored at a low temperature for a long period of time, a resin film obtained by applying the curable resin composition to a substrate, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.
Means for solving the technical problems
Examples of representative embodiments of the present invention are shown below.
< 1 > a curable resin composition comprising:
at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor; and
at least two solvents.
< 2 > the curable resin composition according to < 1 > further comprising a migration inhibitor,
the migration inhibitor is a compound having at least one heterocycle selected from the group consisting of an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring and a triazine ring, and an amino group.
< 3 > the curable resin composition according to < 1 > or < 2 > further comprising a migration inhibitor,
the migration inhibitor is at least one compound selected from the group consisting of 5-methylbenzotriazole, 3-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole and 5-amino-1H-tetrazole.
< 4 > the curable resin composition according to any one of < 1 > to < 3 >, wherein,
the solvent contains dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate is more than 40 mass% relative to the total mass of the solvent, and the content of gamma-butyrolactone is less than 40 mass% relative to the total mass of the solvent.
< 5 > the curable resin composition according to any one of < 1 > to < 4 >, wherein,
the solvent includes a solvent having a nitrogen-containing heterocyclic structure.
< 6 > the curable resin composition according to any one of < 1 > to < 5 >, wherein,
the solvent includes a solvent having an ether bond.
< 7 > the curable resin composition according to any one of < 1 > to < 6 >, wherein,
the content of the solvent having the content of the 2 nd or more among the above solvents is 20 mass% or more based on the total mass of the solvents.
< 8 > the curable resin composition according to any one of < 1 > to < 7 > further comprising a silane coupling agent.
< 9 > the curable resin composition according to any one of < 1 > to < 8 >, wherein,
the curable resin composition is used for at least one storage of a storage container by cold storage at-15 to 16 ℃, and the filling rate of the curable resin composition during the cold storage is 50 to 90 percent relative to the total storage volume of the storage container.
< 10 > the curable resin composition according to any one of < 1 > to < 9 > for use in formation of an interlayer insulating film for a rewiring layer.
< 11 > a resin film obtained by applying the curable resin composition of any one of < 1 > to < 10 > to a substrate.
< 12 > a cured film obtained by curing the curable resin composition of any one of < 1 > to < 10 > or the resin film of < 11 >.
< 13 > a laminate comprising 2 or more layers of the cured film < 12 > and comprising a metal layer between any of the above cured films.
< 14 > a method for producing a cured film, which comprises:
a film forming step of applying the curable resin composition described in any one of < 1 > to < 10 > to a substrate to form a film.
< 15 > the method for producing a cured film according to < 14 > which comprises:
an exposure step of exposing the film and a development step of developing the film.
< 16 > A method for producing a cured film according to < 14 > or < 15 > which comprises:
a heating step of heating the film at 50 to 450 ℃.
< 17 > a semiconductor device comprising < 12 > said cured film or < 13 > said laminate.
Effects of the invention
According to the present invention, there are provided a curable resin composition which is excellent in film thickness uniformity of an obtained resin film even when stored at a low temperature for a long period of time, a resin film obtained by applying the curable resin composition to a substrate, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the embodiments shown.
In the present specification, a numerical range represented by a symbol such as "to" means a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value, respectively.
In the present specification, the term "step" means not only an independent step but also a step which cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved.
With regard to the labeling of the group (atomic group) in the present specification, the label which is not labeled with substituted and unsubstituted includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "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, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include actinic rays or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser light, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".
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 the present specification, the total solid content means the total mass of the components other than the solvent in all the components of the composition. In the present specification, the solid content concentration is a mass percentage of the other components except the solvent with respect to the total mass of the composition.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns, for example. Unless otherwise stated, these molecular weights were determined using THF (tetrahydrofuran) as eluent. And, unless otherwise specified, detection in GPC measurement uses a 254nm wavelength detector of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower", the layer may have another layer on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, the 3 rd layer or the 3 rd element may be further interposed between the layer serving as the reference and the other layer, and the layer serving as the reference and the other layer do not need to be in contact. Also, unless otherwise specified, a direction in which layers are gradually stacked with respect to a substrate is referred to as "up", or, in the case of having a photosensitive layer, a direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction thereof is referred to as "down". The vertical direction is set for convenience of description of the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical direction.
In the present specification, unless otherwise stated, two or more compounds corresponding to each component contained in the composition may be contained in the composition as each component. Also, unless otherwise noted, the content of each ingredient in the composition means the total content of all compounds corresponding to the ingredient.
In this specification, unless otherwise specified, the temperature is 23 ℃, the atmospheric pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50% RH.
In this specification, a combination of preferred embodiments is a more preferred embodiment.
(curable resin composition)
The curable resin composition of the present invention contains at least one resin (hereinafter, also referred to as "specific resin") selected from a polyimide, a polyimide precursor, a polybenzoxazole and a polybenzoxazole precursor, and at least two solvents.
The curable resin composition of the present invention has excellent film thickness uniformity of the obtained resin film even when stored at low temperature for a long period of time.
As a result of the investigation by the present inventors, it has been found that when a curable resin composition containing a solvent alone is stored at a low temperature (for example, 5 ℃ or lower, further-5 ℃ or lower) for a long period of time (for example, 6 months or longer) and then applied to a substrate to form a resin film, the film thickness uniformity of the obtained resin film is poor.
The poor film thickness uniformity of the resin film means that the difference in film thickness between a portion having a small film thickness and a portion having a large film thickness is large in the resin film.
As a result of intensive studies, the present inventors have found that a curable resin composition containing two or more solvents is excellent in film thickness uniformity of a resin film obtained even when stored for a long period of time.
The mechanism by which the above-described effects can be obtained is not clear, but is presumed to be as follows.
When a curable resin composition containing a single solvent alone is stored at low temperature for a long period of time, a component having low solubility in the solvent may precipitate. As described above, it is presumed that when a certain component in the composition is analyzed, a part of the components contained in the composition may be changed due to a local increase in the concentration of other components, a certain reaction being caused, or a component such as a polymerization inhibitor being precipitated and being polymerized.
In this manner, in the composition in which the components are partially changed, even when the precipitates are dissolved again by, for example, heating and stirring after storage, the film thickness uniformity of the resin film is considered to be poor.
However, when the curable resin composition contains two or more solvents, even if the curable resin composition is a component having low solubility in a certain solvent contained in the composition, the curable resin composition may have excellent solubility in other solvents contained in the composition, and the above-mentioned precipitation may be suppressed.
As a result, it is estimated that the change is suppressed and the film thickness uniformity of the resin film after storage is excellent.
Further, it is presumed that when the curable resin composition contains two or more solvents, the deposition of components such as a polymer in the curable resin composition and the change due to the crosslinking of a crosslinkable group in the polymer, a crosslinkable group in a crosslinking agent, and the like are suppressed, and therefore, for example, the resolution when the obtained resin film is subjected to development is easily improved, as compared with the case where the curable resin composition contains one solvent alone, particularly when the curable resin composition is stored at a low temperature for a long period of time.
Further, it is presumed that when the curable resin composition contains two or more solvents, the distribution of the components in the resin film when the resin film is formed tends to be nearly uniform, and the chemical resistance of the obtained cured film tends to be improved, particularly in the case of long-term storage at low temperature, as compared with the case of containing one solvent alone.
The components contained in the curable resin composition of the present invention will be described in detail below.
< solvent >
The curable resin composition of the present invention contains at least two solvents. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, hydrocarbons, sulfoxides, amides, and alcohols.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.
Among these, the ester is preferably an acyclic ester compound from the viewpoint of film thickness uniformity. The acyclic ester compound refers to a compound having no cyclic structure (i.e., lactone structure) containing an ester structure in a molecule.
Examples of the ethers include 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 acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.
Examples of the hydrocarbon include toluene, xylene, anisole, and limonene.
Among these, the hydrocarbon is preferably an aromatic hydrocarbon or a terpene.
Preferable examples of the sulfoxide include dimethyl sulfoxide.
Preferable examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide.
Among these, a compound having a lactam structure or a compound having an ether bond and an amide bond in the structure is more preferable.
Further, as the amide, a commercially available product may be used, and as the commercially available product, an Equamide series (e.g., Equamide B-100, Equamide M-100) manufactured by Idemitsu Kosan Co., Ltd.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl methanol, n-pentanol, methylpentanol, and diacetone alcohol.
The urea preferably includes N, N' -tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, and the like.
Among these, from the viewpoint of film thickness uniformity, the curable resin composition of the present invention preferably contains at least two selected from esters, ethers, ketones, hydrocarbons, sulfoxides and amides, more preferably contains at least two selected from amides and sulfoxides or contains at least one selected from amides and sulfoxides and at least one selected from esters, ethers and hydrocarbons, still more preferably contains at least two selected from amides and sulfoxides or contains at least one selected from amides and sulfoxides and at least one selected from ketones and esters, and particularly preferably contains sulfoxides and esters.
From the viewpoint of resolution (particularly, resolution after long-term storage of the composition at low temperature), the curable resin composition of the present invention preferably contains at least one selected from amides and at least one selected from ketones, and more preferably contains N-methyl-2-pyrrolidone and cyclopentanone.
In the above aspect, the content of the solvent corresponding to the amide-based compound is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvents.
In the above aspect, the content of the solvent corresponding to the ketone is preferably 20 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvents.
In view of the chemical resistance of the obtained cured film (in particular, the chemical resistance of the cured film after the composition is stored at low temperature for a long period of time), the curable resin composition of the present invention preferably contains at least one selected from the group consisting of solvents having an ether bond described later and at least one selected from sulfoxides, more preferably contains a compound having an ether bond and an amide bond in the structure described above and dimethyl sulfoxide, and further preferably contains 3-butoxy-N, N-dimethylpropionamide and dimethyl sulfoxide.
In the above aspect, the content of the amide-based solvent is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvents.
In the above aspect, the content of the solvent corresponding to the sulfoxide is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvent.
Also, from the viewpoint of being able to form a thick resin film, the curable resin composition of the present invention preferably contains at least one selected from solvents having a boiling point of 160 ℃ or higher at 1 atm and at least one selected from solvents having a boiling point of less than 160 ℃ at 1 atm.
Examples of the solvent having a boiling point of 160 ℃ or higher under 1 atm include γ -butyrolactone (204 ℃), dimethyl sulfoxide (189 ℃), N-methyl-2-pyrrolidone (202 ℃), and 3-butoxy-N, N-dimethylpropionamide (215 ℃).
Examples of the solvent having a boiling point of less than 160 ℃ under 1 atm include cyclopentanone (131 ℃), ethyl lactate (154 ℃), and propylene glycol monomethyl ether acetate (146 ℃).
The temperature in parentheses above indicates the boiling point of each solvent at 1 atm.
In the above aspect, the content of the solvent having a boiling point of 160 ℃ or higher at 1 atm is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvent.
In the above aspect, the content of the solvent having a boiling point of less than 160 ℃ under 1 atmospheric pressure is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvent.
The curable resin composition of the present invention preferably contains at least two selected from aprotic solvents or at least one selected from aprotic solvents and at least one selected from protic solvents.
It is considered that the inclusion of the protic solvent in the curable resin composition of the present invention improves the film thickness uniformity when the curable resin composition includes a compound having a salt structure such as an onium salt described later.
Examples of the aprotic solvent include γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N, N-dimethylpropionamide, cyclopentanone, and propylene glycol monomethyl ether acetate.
The protic solvent may be ethyl lactate, for example.
In the above embodiment, the content of the aprotic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total mass of the solvents. The upper limit of the content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
In the above embodiment, the content of the protic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more, based on the total mass of the solvents. The upper limit of the content is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 60% by mass or less.
In addition, it is also one of preferable modes that the aprotic solvent is contained in an amount of 10 to 90 mass% and the protic solvent is contained in an amount of 10 to 90 mass% based on the total mass of the solvents. In the above aspect, the solvent composition preferably contains 20 to 80 mass% of the aprotic solvent and 20 to 80 mass% of the protic solvent, and more preferably contains 40 to 80 mass% of the aprotic solvent and 20 to 60 mass% of the protic solvent.
Further, the curable resin composition of the present invention preferably contains at least one selected from solvents having a molecular weight of 90 or more and at least one selected from solvents having a molecular weight of less than 90, from the viewpoint of being able to form a thick resin film.
In the above aspect, the content of the solvent having a molecular weight of 90 or more is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvents.
In the above aspect, the content of the solvent having a molecular weight of less than 90 is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvent.
From the viewpoint of uniformity of film thickness, the curable resin composition of the present invention preferably contains at least one selected from solvents having an SP value of 21.4MPa or more and at least one selected from solvents having an SP value of less than 21.4 MPa.
Examples of the solvent having an SP value of 21.4MPa or more include γ -butyrolactone (26.3MPa), dimethyl sulfoxide (29.7MPa), N-methyl-2-pyrrolidone (23.1MPa), and 3-butoxy-N, N-dimethylpropionamide (21.5 MPa).
Examples of the solvent having an SP value of less than 21.4MPa include cyclopentanone (21.3MPa), ethyl lactate (20.5MPa), and propylene glycol monomethyl ether acetate (23.1 MPa).
The temperature in parentheses indicates the SP value of each solvent.
In the above aspect, the content of the solvent having an SP value of 21.4MPa or more is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, based on the total mass of the solvent.
In the above aspect, the content of the solvent having an SP value of less than 21.4MPa is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, based on the total mass of the solvent.
From the viewpoint of film thickness uniformity, it is also preferable to use a solvent having an SP value higher than that of a dissolved substance (for example, a specific resin described later) and a solvent having an SP value lower than that of the dissolved substance at the same time.
Further, from the viewpoint of film thickness uniformity, the difference in SP value between the solvent having the highest SP value and the solvent having the lowest SP value among the solvents contained in the curable resin composition of the present invention is preferably 0.2 to 11.5MPa, and more preferably 1.5 to 10.0 MPa.
It is considered that, according to this aspect, since the solubility of various dissolved substances contained in the curable resin composition can be improved, the film thickness uniformity is easily excellent.
In the present invention, the SP value represents the value of the solubility parameter. The SP value in the present invention is based on the hansen solubility parameter: hansen solubility parameters for the formula illustrated in User's Handbook, Second Edition, c.m. hansen (2007), Taylor and Francis Group, llc (hspip manual). Specifically, the SP value was calculated using the "practical hansen solubility parameter HSPiP version 3" (software version 4.0.05) using the following equation.
(SP value) 2 ＝(δHd) 2 +(δHp) 2 +(δHh) 2
Hd: scatter contribution
Hp: polar contribution
Hh: hydrogen bond contribution
Among these, the curable resin composition of the present invention preferably contains at least one solvent selected from the following group a and at least one solvent selected from the following group B or contains at least one solvent selected from the following groups a and B and at least one solvent selected from the following group C.
Group A: dimethyl sulfoxide
Group B: n-methyl-2-pyrrolidone, 3-butoxy-N, N-dimethylpropionamide
Group C: gamma-butyrolactone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate
The group C is more preferably the group C' described below.
A group C': cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate
Among these, as one of preferable embodiments of the curable resin composition of the present invention, there is an embodiment in which the solvent contains dimethyl sulfoxide and ethyl lactate, and the content of ethyl lactate is 40 mass% or more with respect to the total mass of the solvent.
The content of ethyl lactate is preferably 40 to 80% by mass, and more preferably 45 to 60% by mass.
In the above embodiment, the content of γ -butyrolactone is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 10% by mass or less, further preferably 5% by mass or less, and most preferably 1% by mass or less, based on the total mass of the solvent. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
In the above embodiment, the total content of dimethyl sulfoxide and ethyl lactate is preferably 60 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, particularly preferably 90 mass% or more, further preferably 95 mass% or more, and most preferably 99 mass% or more, based on the total mass of the solvent. The upper limit of the total content is not particularly limited, and may be 100 mass%.
The curable resin composition of the present invention preferably contains a solvent having a nitrogen atom in the structure as a solvent, and more preferably contains a solvent having a nitrogen-containing heterocyclic structure.
Examples of the solvent having a nitrogen atom in the structure include the amides.
The solvent having a nitrogen-containing heterocyclic structure is preferably the compound having a lactam structure, and more preferably N-methyl-2-pyrrolidone.
The content of the solvent having a nitrogen atom in the structure is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass, based on the total mass of the solvent.
The curable resin composition of the present invention also preferably contains a solvent having an ether bond as a solvent.
Examples of the solvent having an ether bond include compounds having an ether bond and an amide bond in the structure of the above ethers or amides.
The content of the solvent having an ether bond is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass, based on the total mass of the solvent.
In addition, the content of the solvent having the largest content 2 with respect to the solvent contained in the curable resin composition of the present invention is preferably 20% by mass or more with respect to the total mass of the solvents. The content is preferably 25% by mass or more, more preferably 30% by mass or more, and may be 40% by mass or more.
In the present invention, for example, when the solvent contains 40 mass% of N-methylpyrrolidone, 40 mass% of dimethyl sulfoxide, and 20 mass% of cyclopentanone, the content of the solvent having the content of the component 2 is 40 mass%.
In the curable resin composition of the present invention, the content of water is preferably 5% by mass or less based on the total mass of the solvent, from the viewpoints of suppressing coating defects at the time of coating, improving storage stability, and the like. The content of the water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.
The content of water may be 0 mass%.
From the viewpoint of coatability, the total content of the solvent is preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, more preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 5 to 75% by mass, even more preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 10 to 70% by mass, even more preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 20 to 70% by mass, and even more preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 40 to 70% by mass. The solvent content may be adjusted depending on the desired thickness and coating method.
The curable resin composition of the present invention may contain only two solvents, or may contain three or more solvents.
< specific resin >
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor.
The curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
The specific resin preferably has a radical polymerizable group.
In the case where the specific resin has a radical polymerizable group, the curable resin composition preferably contains a photo radical polymerization initiator described later as a photosensitizer, more preferably contains a photo radical polymerization initiator described later as a photosensitizer and contains a radical crosslinking agent described later, and further preferably contains a photo radical polymerization initiator described later as a photosensitizer, contains a radical crosslinking agent described later and contains a sensitizer described later. A negative photosensitive layer is formed from such a curable resin composition, for example.
The specific resin may have a polarity-converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. Such a curable resin composition is used to form a chemically amplified positive photosensitive layer or negative photosensitive layer, for example.
[ polyimide precursor ]
The type and the like of the polyimide precursor used in the present invention are not particularly limited, but preferably contains a repeating unit represented by the following formula (2).
Formula (2)
[ chemical formula 1]
Figure BDA0003775943360000141
In the formula (2), A 1 And A 2 Each independently represents an oxygen atom or NH, R 111 Represents an organic group having a valence of 2, R 115 Represents a 4-valent organic group, R 113 And R 114 Each independently represents a hydrogen atom or a 1-valent organic group.
A in the formula (2) 1 And A 2 Each independently represents an oxygen atom or NH, preferably an oxygen atom.
R in the formula (2) 111 Represents an organic group having a valence of 2. Examples of the 2-valent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and preferably include a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably contain an aromatic group having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by-Ar-L-Ar-may be exemplified. Wherein Ar is independently an aromatic group, 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 combination of 2 or more of the foregoing. Preferred ranges of these are as described above.
R 111 Preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. One diamine may be used alone, or two or more diamines may be used.
Specifically, the diamine is preferably a diamine containing a group comprising a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing a group comprising an aromatic group having 6 to 20 carbon atoms. Examples of the group containing an aromatic group include the following.
[ chemical formula 2]
Figure BDA0003775943360000151
Wherein A is preferably 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 combination thereof, more 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-SO 2 The group of-is further preferably-CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。
In the formula, a represents a bonding position with another structure.
Specific examples of the diamine include at least one diamine selected from the following: 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1,2-, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-or p-phenylenediamine, diaminotoluene, 4' -or 3,3 ' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -and 3,3 ' -diaminodiphenylmethane, 4' -and 3,3 ' -diaminodiphenylsulfone, 4' -and 3,3 ' -diaminodiphenyl sulfide, 4' -or 3,3 ' -diaminobenzophenone, 3 ' -dimethyl-4, 4' -diaminobiphenyl, 2 ' -dimethyl-4, 4' -diaminobiphenyl, 3 ' -dimethoxy-4, 4' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 '-diaminop-terphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, bis, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 '-diethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-4, 4' -diaminodiphenylmethane, 4 '-diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2, 10-bis (4-aminophenoxy) anthracene, 1, 3' -bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3-bis (4-diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis [ 4-bis (4-amino-phenyl) propane, 4-bis (4-phenyl) propane, 3-bis (4-amino-phenyl) benzene, 3-bis (4-bis) benzene, 3-bis (4-amino-phenyl) benzene, 3-amino-4-amino-phenyl) benzene, 3-phenyl) benzene, 2, 3-bis (4-bis) benzene, 3-bis (4-bis) benzene, 2, 3-bis (4-amino-bis) benzene, 2, 9, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4,4' -tetraaminobiphenyl, 3 ', 4,4' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4,4' -dimethyl-3, 3 ' -diaminodiphenyl sulfone, 3 ', 5,5 ' -tetramethyl-4, 4' -diaminodiphenylmethane, 2, 4-and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, proguanazine, 2,3,5, 6-tetramethyl-p-phenylenediamine, p-phenylene, toluene, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] Hexafluoropropane, 3 ', 5,5 ' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, 2 ', 5,5 ', 6,6 ' -hexafluorotriazine and 4,4' -diamino-p-tetracene.
Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.
Also, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 may be preferably used.
From the viewpoint of flexibility of the obtained organic film, R 111 Preferably represented by-Ar-L-Ar-. Wherein Ar is independently an aromatic group, 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 combination of 2 or more of the foregoing. Ar is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group of 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or-SO 2 -. The aliphatic hydrocarbon group herein is preferably an alkylene group.
And, from the viewpoint of i-ray transmittance, R 111 The organic group having a valence of 2 represented by the following formula (51) or formula (61) is preferable. In particular, from the viewpoint of i-ray transmittance and easy availability, the 2-valent organic group represented by formula (61) is more preferable.
Formula (51)
[ chemical formula 3]
Figure BDA0003775943360000171
In the formula (51), R 50 ～R 57 Each independently a hydrogen atom, a fluorine atom or a 1-valent organic group, R 50 ～R 57 At least 1 of which is a fluorine atom, a methyl group or a trifluoromethyl groupAnd each independently represents a bonding position with the nitrogen atom in the formula (2).
As R 50 ～R 57 The 1-valent organic group in (1) includes 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.
[ chemical formula 4]
Figure BDA0003775943360000172
In the formula (61), R 58 And R 59 Each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound providing the structure of formula (51) or formula (61) include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4, 4' -diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
In addition, the following diamines can also be preferably used.
[ chemical formula 5]
Figure BDA0003775943360000181
R in the formula (2) 115 Represents a 4-valent organic group. The organic group having a valence of 4 is preferably an organic group having a valence of 4 comprising an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
In formula (5) or formula (6), each independently represents a bonding site to another structure.
[ chemical formula 6]
Figure BDA0003775943360000182
In the formula (5), R 112 Preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, or, -CO-、-S-、-SO 2 -and-NHCO-and combinations thereof, more preferably a single bond selected from the group consisting of C1-3 alkylene which may be substituted with fluorine atom, -O-, -CO-, -S-, and-SO 2 The group of (E) is more preferably selected from the group consisting of-CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-, -S-and-SO 2 -2-valent radical in (a).
In particular, R 115 Examples thereof include a tetracarboxylic acid residue remaining after removing an anhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
[ chemical formula 7]
Figure BDA0003775943360000191
In the formula (O), R 115 Represents a 4-valent organic group. R 115 With R in the formula (2) 115 The same meaning, and the same preferable range.
Specific examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenyl sulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9, 10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms.
Further, as preferable examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be cited.
Also preferred is R 111 And R 115 At least one of them has an OH group. More specifically, as R 111 Examples thereof include residues of bisaminophenol derivatives.
R 113 And R 114 Each independently represents a hydrogen atom or a 1-valent organic group, preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group, and more preferably contains a polyalkyleneoxy group. And, preferably R 113 And R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, a radical or the like, and a radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. The radical polymerizable group contained in the polyimide precursor or the like is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III) is preferable.
[ chemical formula 8]
Figure BDA0003775943360000201
In the formula (III), R 200 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In formula (III), a indicates a bonding position to another structure.
In the formula (III), R 201 Represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -or a polyalkyleneoxy group.
Preferred R 201 Examples of (3) include alkylene groups such as vinyl, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene and dodecamethylene, -CH 2 CH(OH)CH 2 -polyalkylene oxide group, more preferably vinyl group, propylene group, trimethylene group, -CH 2 CH(OH)CH 2 The polyalkyleneoxy group is more preferable.
In the present invention, a polyalkyleneoxy group means a group to which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of alkyleneoxy groups of different alkylene groups, the alkyleneoxy groups in the polyalkyleneoxy group may be arranged randomly, may be arranged in a block, or may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferable substituents include alkyl groups, aryl groups, halogen atoms, and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
The polyalkylene oxide group is preferably a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene oxide group, a polytetramethylene oxide group, or a group in which a plurality of ethylene oxide groups and a plurality of propylene oxide groups are bonded, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoint of solvent solubility and solvent resistance. In the group in which a plurality of ethylene oxide groups and a plurality of propylene oxide groups are bonded, the ethylene oxide groups and the propylene oxide groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as an alternating pattern. Preferred modes of repeating the numbers of ethyleneoxy groups and the like in these groups are as described above.
R 113 And R 114 Each independently a hydrogen atom or a 1-valent organic group. Examples of the organic group having a valence of 1 include an aromatic group and an aralkyl group in which an acidic group is bonded to 1, 2 or 3, preferably 1, of carbons constituting an aryl group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acidic group, and the aralkyl group has 7 to 25 carbon atoms and has an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.
R 113 Or R 114 More preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.
From the viewpoint of solubility in organic solvents, R 113 Or R 114 Preferably a 1-valent organic group. The 1-valent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain or branched alkyl group include 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, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl 2- (2- (2-methoxyethoxy) ethoxy group, a 2- (2- (2-ethoxyethoxy) ethoxy group, a 2- (2- (2-methoxyethoxy) ethoxy group, and a 2- (2- (2- (2-ethoxyethoxy) ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoroyl, dicyclohexyl, and sterenyl. Among them, cyclohexyl is most preferable from the viewpoint of achieving both high sensitivity. The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described later.
The aromatic group is specifically a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, benzodiindene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, tetracene ring, perylene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, perylene ring, pentacene ring, acenaphthylene ring, anthracene ring, perylene ring, pentacene ring, perylene ring, acenaphthylene ring, anthracene ring, perylene ring, or aromatic ring, aromatic ring,
Figure BDA0003775943360000221
A ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, a benzopyran ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. Benzene rings are most preferred.
In the formula (2), in R 113 In the case of a hydrogen atom or in R 114 In the case of a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
R 113 And R 114 At least one of them may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal group, ketal group, silyl ether group, tertiary alkyl ester group and the like are preferable from the viewpoint of exposure sensitivity From the viewpoint of the above, acetal groups are more preferable.
Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferable.
Also, the polyimide precursor preferably has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
The polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by formula (2-a). With such a configuration, the width of the exposure latitude can be further increased.
Formula (2-A)
[ chemical formula 9]
Figure BDA0003775943360000231
In the formula (2-A), A 1 And A 2 Represents an oxygen atom, R 111 And R 112 Each independently represents an organic group having a valence of 2, R 113 And R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 And R 114 At least one of them is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
A 1 、A 2 、R 111 、R 113 And R 114 Independently of one another in formula (2)A 1 、A 2 、R 111 、R 113 And R 114 The same meanings as defined above, and the same preferred ranges.
R 112 And R in the formula (5) 112 The same meanings as defined above, and the same preferred ranges.
The polyimide precursor may contain one kind of the repeating unit represented by formula (2), or may contain two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (2) may be contained. It goes without saying that the polyimide precursor may contain other kinds of repeating units in addition to the repeating unit of the formula (2).
An embodiment of the polyimide precursor of the present invention is a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all the repeating units are repeating units represented by the formula (2).
The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersion degree of the molecular weight of the polyimide precursor is not particularly limited, and is, for example, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, further preferably 3.2 or less, further preferably 3.1 or less, further preferably 3.0 or less, and particularly preferably 2.95 or less.
On the other hand, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000, from the viewpoint of developability. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
The dispersion of the molecular weight of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more, from the viewpoint of developability. The upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less.
In the present specification, the degree of dispersion of molecular weights is a value calculated using weight average molecular weight/number average molecular weight.
[ polyimide ]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developer mainly composed of an organic solvent.
In the present specification, an alkali-soluble polyimide means a polyimide in which 0.1g or more is dissolved at 23 ℃ in 100g of a 2.38 mass% aqueous tetramethylammonium solution, and from the viewpoint of pattern formability, 0.5g or more is preferably dissolved, and 1.0g or more is more preferably dissolved. The upper limit of the amount of the above-mentioned solvent is not particularly limited, but is preferably 100g or less.
In view of the film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In the present specification, "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" refers to other bonding chains.
Fluorine atom-
The polyimide preferably has a fluorine atom from the viewpoint of the film strength of the obtained organic film.
Fluorine atom is preferably contained in R in the repeating unit represented by the following formula (4), for example 132 Or R in a repeating unit represented by the following formula (4) 131 Among these, R contained as a fluorinated alkyl group in a repeating unit represented by the following formula (4) is more preferable 132 Or R in a repeating unit represented by the following formula (4) 131 In (1).
The amount of fluorine atoms is preferably 1 to 50mol/g, more preferably 5 to 30mol/g, based on the total mass of the polyimide.
Silicon atom-
The polyimide preferably has a silicon atom from the viewpoint of the film strength of the obtained organic film.
Silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described later 131 Among these, R contained as an organically modified (poly) siloxane structure described later in a repeating unit represented by the formula (4) described later is more preferable 131 In (1).
The silicon atom or the organically modified (poly) siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.
The amount of the silicon atom is preferably 0.01 to 5mol/g, more preferably 0.05 to 1mol/g, based on the total mass of the polyimide.
-ethylenic unsaturation-
The polyimide preferably has an ethylenically unsaturated bond from the viewpoint of the film strength of the obtained organic film.
The polyimide may have an ethylenically unsaturated bond at the terminal of the main chain or an ethylenically unsaturated bond in the side chain, but preferably has an ethylenically unsaturated bond in the side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the formula (4) described later 132 Or R in a repeating unit represented by the following formula (4) 131 Of these, R contained as a group having an ethylenically unsaturated bond in a repeating unit represented by the following formula (4) is more preferable 132 Or R in a repeating unit represented by the following formula (4) 131 In (1).
Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later 131 Of these, R contained as a group having an ethylenically unsaturated bond in a repeating unit represented by the following formula (4) is more preferable 131 In (1).
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group, which may be substituted, such as a vinyl group, an allyl group, or a vinylphenyl group, which is directly bonded to an aromatic ring, (meth) acrylamide group, (meth) acryloyloxy group, and a group represented by the following formula (IV).
[ chemical formula 10]
Figure BDA0003775943360000251
In the formula (IV), R 20 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In the formula (IV), R 21 Represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C (═ O) O-, -O (C ═ O) NH-, a (poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3 carbon atoms, and the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), or a combination of 2 or more of these.
Among these, R 21 The group represented by any of the following formulae (R1) to (R3) is preferable, and the group represented by formula (R1) is more preferable.
[ chemical formula 11]
Figure BDA0003775943360000261
In the formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group obtained by bonding 2 or more of these groups, X represents an oxygen atom or a sulfur atom, and represents a bonding position with another structure, ● represents a bonding position with R in the formula (III) 201 The bonding position of the bonded oxygen atom.
Preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms in L in the formulae (R1) to (R3) are the same as those described above for R 21 The preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms in (B) is the same.
In the formula (R1), X is preferably an oxygen atom.
In the formulae (R1) to (R3), the same meanings as in the formula (IV) apply, and preferred embodiments are also the same.
The structure represented by the formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).
The structure represented by the formula (R3) can be obtained by, for example, reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).
In formula (IV), one represents a bonding site to another structure, preferably a bonding site to a main chain of polyimide.
The amount of the ethylenically unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, based on the total mass of the polyimide.
Crosslinkable groups other than ethylenically unsaturated bonds
The polyimide may have a crosslinkable group other than an ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group or an oxetane group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in, for example, R in the repeating unit represented by the formula (4) described later 131 In (1).
The amount of the crosslinkable group other than the ethylenically unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, based on the total mass of the polyimide.
-polarity inverting group-
The polyimide may have a polarity-converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 And R 114 The acid-decomposable groups mentioned in (1) are the same, and preferred embodiments are the same。
Acid value-
When the polyimide is subjected to alkali development, the acid value of the polyimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of improving the developability.
The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, solvent development described later), the acid value of the polyimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and still more preferably 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, according to JIS K0070: 1992, the procedure described in the section of paper.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably an acid group having a pKa of 3 to 8, from the viewpoint of both storage stability and developability.
pKa is expressed in terms of its negative common logarithm pKa in view of the dissociation reaction that releases hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Also, reference may be made to the values disclosed in "revised base edition of chemical handbook, 5 th edition" compiled by the Japan chemical society.
Alternatively, when the acid group is a polybasic acid such as phosphoric acid, the pKa is the first dissociation constant.
The polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group as such an acid group.
Phenolic hydroxyl group-
The polyimide preferably has a phenolic hydroxyl group from the viewpoint of optimizing the development speed by an alkali developing solution.
The polyimide may have a phenolic hydroxyl group at a terminal of a main chain or may have a phenolic hydroxyl group in a side chain.
The phenolic hydroxyl group is preferably contained in R in a repeating unit represented by the following formula (4), for example 132 Or R in a repeating unit represented by the following formula (4) 131 In (1).
The amount of the phenolic hydroxyl group is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, based on the total mass of the polyimide.
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and more preferably contains a repeating unit represented by the formula (4) and has a polymerizable group.
Formula (4)
[ chemical formula 12]
Figure BDA0003775943360000281
In the formula (4), R 131 Represents an organic group having a valence of 2, R 132 Represents a 4-valent organic group.
When having a polymerizable group, the polymerizable group may be located at R 131 And R 132 At least one of the above-mentioned groups may be located at the end of the polyimide, as represented by the following formula (4-1) or formula (4-2).
Formula (4-1)
[ chemical formula 13]
Figure BDA0003775943360000282
In the formula (4-1), R 133 The other groups are the same as those of the formula (4).
Formula (4-2)
[ chemical formula 14]
Figure BDA0003775943360000291
R 134 And R 135 At least one of them is a polymerizable group inThe organic group is not a polymerizable group, and the other groups have the same meaning as in formula (4).
The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor and the like.
R 131 Represents an organic group having a valence of 2. As the 2-valent organic group, R in the formula (2) can be illustrated 111 The same groups, and the same preferred ranges, are also applicable.
And as R 131 Examples thereof include diamine residues remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cyclic aliphatic, and aromatic diamines. Specific examples thereof include R in the formula (2) of the polyimide precursor 111 Examples of (3).
From the viewpoint of more effectively suppressing the occurrence of warpage during calcination, R 131 Diamine residues having at least 2 alkylene glycol units in the backbone are preferred. More preferably, the diamine residue contains 2 or more ethylene glycol chains or propylene glycol chains in total or both of 1 molecule, and still more preferably the diamine residue does not contain an aromatic ring.
Examples of the diamine containing 2 or more ethylene glycol chains and propylene glycol chains in total in 1 molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name: HUNTSMAN Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-amine, but the diamine is not limited thereto.
R 132 Represents a 4-valent organic group. As the organic group having a valence of 4, R in the formula (2) may be exemplified 115 The same groups, and the same preferred ranges, are also provided.
For example, as R 115 And 4 bonds of the exemplified organic group having a valence of 4 are bonded to 4-C (═ O) -moieties in the above formula (4) to form a condensed ring.
And, R 132 May be derived from tetracarboxylic dianhydridesTetracarboxylic acid residue remaining after removing the anhydride group, and the like. Specific examples thereof include R in the formula (2) of the polyimide precursor 115 Examples of (3). From the viewpoint of the strength of the organic film, R 132 Preferably an aromatic diamine residue having 1 to 4 aromatic rings.
Also preferred is R 131 And R 132 At least one of them has an OH group. More specifically, as R 131 Preferable examples thereof include 2, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and the above-mentioned (DA-1) to (DA-18) s as R 132 More preferred examples thereof include the above-mentioned (DAA-1) to (DAA-5).
Further, the polyimide also preferably has a fluorine atom in the structure. The content of the fluorine atom in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
For the purpose of improving adhesion to a substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
In order to improve the storage stability of the composition, it is preferable to seal the main chain ends of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, or a mono-active ester compound. Among these, monoamines are more preferably used, and preferable examples of the monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 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, 3-ethynylaniline, 4-ethynylaniline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, and mixtures thereof, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, and the like. These may be used in two or more kinds, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.
Imidization rate (ring-closure rate) -
The imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more, from the viewpoint of film strength, insulation property, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited, and may be 100% or less.
The imidization ratio is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide was measured, and 1377cm as an absorption peak derived from the imide structure was obtained -1 Near peak intensity P1. Then, the polyimide was heat-treated at 350 ℃ for 1 hour, and the infrared absorption spectrum was measured again to determine 1377cm -1 Near peak intensity P2. The imidization ratio of the polyimide was determined from the following formula using the obtained peak intensities P1 and P2.
Imidization ratio (%) (peak strength P1/peak strength P2) × 100
The polyimides may all contain one species of R 131 Or R 132 The repeating unit of the above formula (4) may contain 2 or more different kinds of R 131 Or R 132 The repeating unit of the above formula (4). The polyimide may contain other types of repeating units in addition to the repeating unit of formula (4).
The polyimide can be synthesized, for example, by the following method: a method of reacting a tetracarboxylic dianhydride with a diamine compound (a capping agent in which a part is substituted with a monoamine) at a low temperature; a method of reacting a tetracarboxylic dianhydride (a capping agent in which a part is substituted with an acid anhydride or a monochloride compound or a mono-active ester compound) with a diamine compound at a low temperature; a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then reacted with a diamine (an end-capping agent in which a part is substituted with a monoamine) in the presence of a condensing agent; a method in which a polyimide precursor is obtained by a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is chlorinated and reacted with a diamine (a blocking agent in which a portion is substituted with a monoamine), and the polyimide precursor is completely imidized by a known imidization method; alternatively, a method of stopping the imidization reaction in the middle and introducing a part of the imide structure; and a method of introducing a part of imide structure by mixing a completely imidized polymer with the polyimide precursor.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM co., ltd.) and Matrimide5218 (manufactured by HUNTSMAN corporation).
The polyimide preferably has a weight average molecular weight (Mw) of 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, at least one kind of polyimide preferably has a weight average molecular weight within the above range.
On the other hand, the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000, from the viewpoint of chemical resistance.
[ polybenzoxazole precursor ]
The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but preferably include a repeating unit represented by the following formula (3).
Formula (3)
[ chemical formula 15]
Figure BDA0003775943360000321
In the formula (3), R 121 Represents an organic group having a valence of 2, R 122 Represents a 4-valent organic group, R 123 And R 124 Each independently represents a hydrogen atom or a 1-valent organic group.
In the formula (3), R 123 And R 124 Are respectively reacted with R in the formula (2) 113 The same meanings as defined above, and the same preferred ranges. That is, at least one is preferably a polymerizable group.
In the formula (3), R 121 Represents an organic group having a valence of 2. The organic group having a valence of 2 is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. R 121 Dicarboxylic acid residues are preferred. The dicarboxylic acid residue may be used alone or in combination of two or more.
As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferable, and dicarboxylic acid residues containing an aromatic group are more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and 2 — COOH is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,6, 6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorsebacic acid, 1, 9-azelaic acid, dodecanedioic acid, and mixtures thereof, Tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, tridecanedioic acid, hentriacontanedioic acid, diglycolic acid (diglycolic acid), and the like.
[ chemical formula 16]
Figure BDA0003775943360000331
(wherein Z is a C1-6 hydrocarbon group, and n is an integer of 1-6.)
As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferable, and the following dicarboxylic acids including only a group having an aromatic group and 2 — COOH are more preferable.
[ chemical formula 17]
Figure BDA0003775943360000332
Wherein A represents a group selected from-CH 2 -、-O-、-S-、-SO 2 -、-CO-、-NHCO-、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 The 2-valent groups in (a) represent the bonding sites with other structures, respectively and independently.
Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether, and terephthalic acid.
In the formula (3), R 122 Represents a 4-valent organic group. As the 4-valent organic group, with R in the above formula (2) 115 The same meaning, and the same preferable range.
R 122 Also preferred are groups derived from bisaminophenol derivatives, as derived from bisaminesExamples of the group of the phenylphenol derivative include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenylsulfone, 4 '-diamino-3, 3' -dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, and mixtures thereof, 2, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.
Among bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.
[ chemical formula 18]
Figure BDA0003775943360000341
In the formula, X 1 represents-O-, -S-, -C (CF) 3 ) 2 -、-CH 2 -、-SO 2 -, -NHCO-, +, and #, respectively, represent bonding sites to other structures. R represents a hydrogen atom or a substituent having a valence of 1, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And, R 122 The structure represented by the above formula is also preferable. At R 122 In the case of the structure represented by the above formula, in the total of 4 and #, preferably, any 2 are the same as R in the formula (3) 122 The bonding position of the bonded nitrogen atom and the other 2 are R in the formula (3) 122 The bonding position of the bonded oxygen atom, more preferably 2, is bonded to R in the formula (3) 122 The bonding position of the bonded oxygen atom and 2 # s are bonded to R in the formula (3) 122 The bonding position of the bonded nitrogen atom, or 2 is R in the formula (3) 122 Bound nitrogen atomThe 2 # s are bonded to R in the formula (3) 122 The bonding position of the bonded oxygen atom, more preferably 2, is R in the formula (3) 122 The bonding position of the bonded oxygen atom and 2 # s are bonded to R in the formula (3) 122 The bonding position of the bonded nitrogen atom.
[ chemical formula 19]
Figure BDA0003775943360000351
In the formula (A-s), R 1 Is hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). R 2 Any of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group and a cyclic alkyl group may be the same or different. R 3 The alkyl group may be the same or different and is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group.
[ chemical formula 20]
Figure BDA0003775943360000352
(in the formula (A-sc), represents the aromatic ring bond with the aminophenol group of the bisaminophenol derivative represented by the formula (A-s).)
In the above formula (A-s), it is considered that R is in the ortho position to the phenolic hydroxyl group 3 The above substituent is also preferable from the viewpoint of further increasing the effect of increasing the cyclization ratio at the time of curing at low temperature, since the carbonyl carbon of the amide bond is closer to the hydroxyl group.
And, in the above formula (A-s), R 2 Is alkyl and R 3 The alkyl group is preferable because it can maintain the effects of high transparency to i-rays and high cyclization ratio at low temperature curing.
And, in the above formula (A-s), R 1 Further preferred is an alkylene group or a substituted alkylene group. As R 1 Alkylene and substituted alkylene ofExamples thereof include linear or branched alkyl groups having 1 to 8 carbon atoms, and among these, the precursor of polybenzoxazole having a sufficient solubility in a solvent and an excellent balance is more preferable from the viewpoint that a polybenzoxazole precursor having a high transparency to i-rays and a high cyclization ratio at the time of curing at a low temperature can be obtained while maintaining the effect of high transparency to i-rays 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -。
As the method for producing the bisaminophenol derivative represented by the formula (A-s), for example, see the paragraphs 0085 to 0094 and example 1 (paragraphs 0189 to 0190) of Japanese patent laid-open publication No. 2013-256506, which are incorporated herein by reference.
Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include the structures described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, the contents of which are incorporated herein. Needless to say, the present invention is not limited to these examples.
The polybenzoxazole precursor may also contain other kinds of repeating units in addition to the repeating unit of the above formula (3).
From the viewpoint of suppressing the occurrence of warpage accompanying the ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating unit.
[ chemical formula 21]
Figure BDA0003775943360000361
In the formula (SL), Z has a structure a and a structure b, R 1s Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s Is a hydrocarbon group of 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At least 1 of them is an aromatic group, and the others are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be a block polymerization or a random polymerization. The molar% of the Z moiety is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
In the formula (SL), preferable Z is R in the structure of b 5s And R 6s Z being phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. When the molecular weight is within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and the effect of suppressing warpage and the effect of improving the solubility of the solvent can be achieved at the same time.
When the diamine residue represented by the formula (SL) is contained as another kind of repeating unit, it is also preferable that the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride is further contained as a repeating unit. Examples of such tetracarboxylic acid residues include R in the formula (2) 115 Examples of (3).
For example, in the case where a polybenzoxazole precursor is used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersion degree of the molecular weight of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.
[ polybenzoxazole ]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. The compound may be a compound represented by the following formula (X) and having a polarity-converting group such as an acid-decomposable group.
[ chemical formula 22]
Figure BDA0003775943360000371
In the formula (X), R 133 Represents an organic group having a valence of 2, R 134 Represents a 4-valent organic group.
When the polar group has a polymerizable group or an acid-decomposable group or the like, the polar group may be located at R 133 And R 134 At least one of them may be located at the end of the polybenzoxazole as represented by the following formula (X-1) or formula (X-2).
Formula (X-1)
[ chemical formula 23]
Figure BDA0003775943360000372
In the formula (X-1), R 135 And R 136 At least one of them is a polar converting group such as a polymerizable group or an acid-decomposable group, and if not a polar converting group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meaning as in the formula (X).
Formula (X-2)
[ chemical formula 24]
Figure BDA0003775943360000381
In the formula (X-2), R 137 The other groups are substituents, and the other groups have the same meanings as in the formula (X).
The polarity-converting group such as a polymerizable group or an acid-decomposable group has the same meaning as that of the polymerizable group described above for the polymerizable group of the polyimide precursor and the like.
R 133 Represents an organic group having a valence of 2. Examples of the organic group having a valence of 2 include an aliphatic group and an aromatic group. Specific examples thereof include those of the polybenzoxazole precursor represented by the formula (3)R 121 Examples of (c). Preferred examples thereof are the same as those of R 121 The same is true.
R 134 Represents a 4-valent organic group. Examples of the organic group having a valence of 4 include R in the formula (3) of the polybenzoxazole precursor 122 Examples of (3). Preferred examples thereof are the same as those of R 122 The same is true.
For example, as R 122 The 4 bonds of the exemplified organic group having a valence of 4 are bonded to the nitrogen atom and the oxygen atom in the formula (X) to form a condensed ring. For example, at R 134 In the case of the following organic group, the following structure is formed.
[ chemical formula 25]
Figure BDA0003775943360000382
The oxazole conversion of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the ratio of the oxazole conversion is 85% or more, film shrinkage due to a closed loop generated during the oxazole conversion by heating is reduced, and the occurrence of warpage can be more effectively suppressed.
The polybenzoxazole can all contain a single species comprising one R 131 Or R 132 The repeating unit of the formula (X) may contain 2 or more different kinds of R 131 Or R 132 The repeating unit of the above formula (X). The polybenzoxazole may contain other kinds of repeating units in addition to the repeating unit of the formula (X).
With regard to polybenzoxazoles, for example, by reacting bisaminophenol derivatives with a compound containing R 133 The precursor of polybenzoxazole can be obtained by reacting a dicarboxylic acid (or a dicarboxylic acid dichloride) of the above dicarboxylic acid with a dicarboxylic acid derivative or the like to obtain a polybenzoxazole precursor and then subjecting the precursor to an oxazole reaction by a known oxazole reaction method.
In the case of dicarboxylic acids, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1, 2, 3-benzotriazole or the like can be used in order to improve the reaction yield or the like.
The polybenzoxazole preferably has a weight average molecular weight (Mw) of 5,000 to 70,000, more preferably 8,000 to 50,000, further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more polybenzoxazoles are contained, the weight average molecular weight of at least one polybenzoxazole is preferably within the above range.
[ method for producing polyimide precursor or the like ]
Polyimide precursors and the like are obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. Preferably, the compound is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the resulting product with a diamine.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in carrying out the reaction. The organic solvent may be one kind or two or more kinds.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
The polyimide may be produced by cyclizing the polyimide by a method such as thermal imidization or chemical imidization (for example, a cyclization reaction is promoted by allowing a catalyst to act) after the synthesis of the polyimide precursor, or may be directly synthesized.
It is also preferable to carry out the synthesis using a non-halogen catalyst instead of the halogenating agent. The non-halogen catalyst may be a known amidation catalyst containing no halogen atom, and examples thereof include boroxine (boroxine) compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N, N '-diisopropylcarbodiimide, N' -dicyclohexylcarbodiimide, and the like.
Blocking agents
In the method for producing a polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the ends of the polyimide precursor or the like with a sealing agent such as an acid anhydride, a monocarboxylic acid, a monochloride compound, a mono-active ester compound or the like. As the blocking agent, monohydric alcohol, phenol, thiol, thiophenol, and monoamine are more preferably used.
Preferred examples of the monohydric alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, primary alcohols such as 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as tert-butyl alcohol and adamantanol. Preferred examples of the phenol compound include phenol, methoxyphenol, methylphenol, naphthalen-1-ol, and naphthalen-2-ol.
Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 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, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, and the like, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. These may be used in two or more kinds, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.
In addition, when the amino group at the end of the resin is sealed, the resin can be sealed with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and carboxylic acid anhydrides and carboxylic acid chlorides are more preferred. Preferred compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and benzoic anhydride. Preferred examples of the carboxylic acid chloride include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
Solid precipitation-
The production of the polyimide precursor or the like may include a step of precipitating a solid. Specifically, the polyimide precursor and the like in the reaction solution are precipitated in water, and dissolved in a soluble solvent such as a polyimide precursor and the like such as tetrahydrofuran, whereby solid deposition can be performed.
Then, the polyimide precursor and the like are dried to obtain a powdery polyimide precursor and the like.
[ content ]
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more, based on the total solid content of the composition. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the composition.
The composition of the present invention may contain only one specific resin, or may contain two or more types. When two or more kinds are contained, the total amount is preferably in the above range.
< other resins >
The composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "other resin").
Examples of the other resin include polyamideimide, a polyamideimide precursor, a phenol resin, polyamide, an epoxy resin, polysiloxane, a resin having a siloxane structure, an acrylic resin, and the like.
For example, by further adding an acrylic resin, a composition excellent in coatability can be obtained, and an organic film excellent in solvent resistance can be obtained.
For example, by adding an acrylic resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described below, the coatability of the composition, the solvent resistance of the organic film, and the like can be improved.
When the 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, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, based on the total solid content of the composition.
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, based on the total solid content of the composition.
In addition, as a preferred embodiment of the composition of the present invention, a mode in which the content of the other resin is low can be also adopted. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less, based on the total solid content of the composition. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more are included, the total amount is preferably within the above range.
< photosensitizers >
The compositions of the present invention preferably comprise a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.
[ photopolymerization initiator ]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, the active agent may be an active agent that generates an active radical by acting on a sensitizer excited by light.
The photo radical polymerization initiator is preferably an oxime compound described later.
The photo radical polymerization initiator preferably contains at least one compound having at least about 50L/mol in the range of about 300 to 800nm (preferably 330 to 500nm) -1 /cm -1 A compound having a molar absorptivity of (a). The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer (spectrophotometer) manufactured by Varian corporation) using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like. The details of these can be found in paragraphs 0165 to 0182 of Japanese patent laid-open publication No. 2016-027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219, which are incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which is incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku co.
In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184(IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: manufactured by BASF) were used.
As the aminoacetophenone-based initiator, the compound described in Japanese patent laid-open No. 2009-191179, which has an absorption maximum wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.
Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: manufactured by BASF) can be used as a commercially available product.
Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF corporation).
The photo radical polymerization initiator may more preferably be an oxime compound. By using the oxime compound, the exposure latitude can be more effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.
Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-p-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.
Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photo radical polymerization initiator 2 described in Japanese patent application laid-open No. 2012 and 014052) can be preferably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Also, DFI-091 (manufactured by Daito Chemix Corporation) can be used.
Oxime compounds of the following structure can also be used.
[ chemical formula 26]
Figure BDA0003775943360000441
Further, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.
Most preferred examples of the oxime compound include an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and 2009-191061.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-ben-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.
The photo radical polymerization initiator is preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound and an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α -aminoketone compound, an oxime compound, a triarylimidazole dimer and a benzophenone compound, still more preferably a metallocene compound or an oxime compound, and still more preferably an oxime compound.
Further, as the photo radical polymerization initiator, there can be used N, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, alkylanthraquinone and other aromatic condensed rings, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.
[ chemical formula 27]
Figure BDA0003775943360000451
In the formula (I), R I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, and a phenyl group or a biphenyl group substituted with at least 1 of the alkyl groups having 1 to 4 carbon atoms, R I01 Is a group of the formula (II) or is a group of the formula (II) with R I00 Same radicals, R I0 2～R I04 Each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen atom.
[ chemical formula 28]
Figure BDA0003775943360000461
In the formula, R I05 ～R I07 With R of the above formula (I) I0 2～R I04 The same is true.
Further, as the photo radical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469 can be used.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, even more preferably 1.0 to 10% by mass, based on the total solid content of the composition of the present invention. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.
[ photoacid generators ]
Also, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing the photoacid generator, for example, an acid is generated in an exposed portion of the composition layer, and the solubility of the exposed portion in a developing solution (for example, an alkaline aqueous solution) is increased, whereby a positive pattern in which the exposed portion is removed by the developing solution can be obtained.
Further, the following method can be adopted: when the composition contains a photoacid generator and a polymerizable compound other than a radical polymerizable compound, which will be described later, for example, the crosslinking reaction of the polymerizable compound is accelerated by an acid generated in an exposed portion, so that the exposed portion is less likely to be removed by a developer than a non-exposed portion. According to such a manner, a negative pattern can be obtained.
The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include onium salt compounds such as quinone diazide, diazonium salts, phosphonium salts, sulfonium salts and iodine salts, and sulfonate compounds such as imide sulfonate, oxime sulfonate, diazodisulfone, disulfone and o-nitrobenzyl sulfonate.
Examples of the quinonediazide include a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide, and a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with a quinonediazido group.
In the present invention, any of 5-naphthoquinonediazidosulfonyl group and 4-naphthoquinonediazidosulfonyl group can be preferably used as the quinonediazide. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl ester compound was extended to the g-ray region of the mercury lamp, which was suitable for g-ray exposure. In the present invention, it is preferable that the 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound are selected according to the exposure wavelength. Further, the naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or the 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound may be contained.
The naphthoquinone diazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazides, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide include 1, 2-naphthoquinone-2-diazide-5-sulfonic acid, 1, 2-naphthoquinone-2-diazide-4-sulfonic acid, and salts and ester compounds of these compounds.
The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), the following formula (OS-103), the following formula (OS-104) or the following formula (OS-105).
[ chemical formula 29]
Figure BDA0003775943360000471
In the formula (OS-1), X 3 Represents an alkyl group, an alkoxy group or a halogen atom. In the presence of multiple X 3 In the case of (3), the same or different may be used. X is above 3 The alkyl group and the alkoxy group in (1) may have a substituent. As the above X 3 The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. As the above X 3 The alkoxy group in (3) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. As the above X 3 The halogen atom in (1) is preferably a chlorine atom or a fluorine atom.
In the formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, plural X' s 3 May be the same or different.
In the formula (OS-1), R 34 Represents an alkyl group or an aryl group, and is preferably 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, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W, or an anthracenyl group which may be substituted by W. W represents a halogen atom, a cyano group, Nitro, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms or halogenated alkoxy with 1-5 carbon atoms, aryl with 6-20 carbon atoms, and halogenated aryl with 6-20 carbon atoms.
In the formula (OS-1), m3 is particularly preferably 3, X 3 Is methyl, X 3 The substitution position of (A) is ortho, R 34 A linear alkyl group having 1 to 10 carbon atoms, a 7, 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group.
Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in the paragraphs 0064 to 0068 of Japanese patent laid-open publication No. 2011-209692 and 0158 to 0167 of Japanese patent laid-open publication No. 2015-194674, which are incorporated herein.
[ chemical formula 30]
Figure BDA0003775943360000481
In the formulae (OS-103) to (OS-105), R s1 Represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R may be present s2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and there may be a plurality of R s6 Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6.
In the formulae (OS-103) to (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) may have a substituent T.
In the formulae (OS-103) to (OS-105), R s2 Preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. In the compound, 2 or more R may be present s2 Of these, 1 or 2 are preferably an alkyl group, an aryl group or a halogen atom, more preferably 1 is an alkyl group, an aryl group or a halogen atom, particularly preferably 1 is an alkyl group and the remainder are hydrogen atomsAnd (4) adding the active ingredients. R s2 The alkyl group or the aryl group represented may have a substituent T.
In the formula (OS-103), the formula (OS-104) or the formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
In the formulae (OS-103) to (OS-105), ns represents 1 or 2, ns is preferably 1 in the case where Xs is O, and ns is preferably 2 in the case where Xs is S.
In the formulae (OS-103) to (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) may have a substituent.
In the formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
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), the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).
[ chemical formula 31]
Figure BDA0003775943360000491
In the formulae (OS-106) to (OS-111), R t1 Represents alkyl, aryl or heteroaryl, R t7 Represents a hydrogen atom or a bromine atom, R t8 Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R t9 Represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R t2 Represents a hydrogen atom or a methyl group.
In the formulae (OS-106) to (OS-111), R t7 Represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
In the formulae (OS-106) to (OS-111), R t8 Represents a hydrogen atom or a carbon atom having 1 to 8The alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group of (A) is preferably an alkyl group, halogen atom or phenyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.
In the formulae (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, preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime may have either one or a mixture of the three-dimensional structures (E, Z).
Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include those described in paragraphs 0088 to 0095 of Japanese patent laid-open publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese patent laid-open publication No. 2015-194674, which are incorporated herein by reference.
As a preferred other embodiment of the oxime sulfonate compound containing at least 1 oxime sulfonate group, there can be mentioned compounds represented by the following formulae (OS-101) and (OS-102).
[ chemical formula 32]
Figure BDA0003775943360000501
In the formula (OS-101) or the formula (OS-102), R u9 Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. More preferably R u9 In the form of cyano or aryl, R is more preferably u9 In cyano, phenyl or naphthyl form.
In the formula (OS-101) or the formula (OS-102), R u2a Represents an alkyl group or an aryl group.
In the formula (OS-101) or the formula (OS-102), Xu represents-O-, -S-, -NH-, -NR- u5 -、-CH 2 -、-CR u6 H-or CR u6 R u7 -，R u5 ～R u7 Each independently represents an alkyl group or an aryl group.
In the formula (OS-101) or the formula (OS-102), R u1 ～R u4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group. R u1 ～R u4 2 of which may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with the benzene ring. As R u1 ～R u4 Preferably a hydrogen atom, a halogen atom or an alkyl group, and also preferably R u1 ～R u4 At least 2 of which are bonded to each other to form an aryl group. Among them, R is preferred u1 ～R u4 All by way of hydrogen atoms. The above-mentioned substituents may each have a substituent.
The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the oxime sulfonate compound, the three-dimensional structures (E, Z, etc.) of the oxime or benzothiazole ring may be either one of them or a mixture thereof.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in the paragraphs No. 0102 to No. 0106 of Japanese patent application laid-open No. 2011-209692 and the paragraphs No. 0195 to 0207 of Japanese patent application laid-open No. 2015-194674, and these contents are incorporated in the present specification.
Among the above compounds, the following compounds b-9, b-16, b-31 and b-33 are preferred.
[ chemical formula 33]
Figure BDA0003775943360000511
Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of Japanese patent application laid-open No. 2008-013646.
In addition, commercially available products can be used as the photoacid generator. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (both manufactured by FUJIFILM Wako pure chemical Corporation), Omnicat 250, Omnicat 270 (both manufactured by IGM Resins B.V., Inc.), Irgacure 250, Irgacure 270, Irgacure 290 (both manufactured by BASF Co., Ltd.), and MBZ-101(Midori Kagaku Co., Ltd.).
Further, preferred examples thereof include compounds represented by the following structural formulae.
[ chemical formula 34]
Figure BDA0003775943360000521
As the photoacid generator, an organic halide can also be applied. Specific examples of the organic halide include compounds described in "Bull chem. Soc Japan" 42, 2924(1969), U.S. Pat. No. 3,905,815, Japanese Kokoku publication No. 46-4605, Japanese Kokai publication No. 48-36281, Japanese Kokai publication No. 55-32070, Japanese Kokai publication No. 60-239736, Japanese Kokai publication No. 61-169835, Japanese Kokai publication No. 61-169837, Japanese Kokai publication No. 62-58241, Japanese Kokai publication No. 62-212401, Japanese Kokai publication No. 63-70243, Japanese Kokai publication No. 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No. 3), (1970), etc., and particularly trihalomethyl-substituted oxazole compounds: an S-triazine compound.
More preferably, the s-triazine derivative is one in which at least 1 mono-, di-or trihalomethyl group is bonded to the s-triazine ring, and specific examples thereof include 2,4, 6-tris (monochloromethyl) -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- (. alpha.,. beta. -trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, and the like, 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-isopropoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyloxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4, 6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4, 6-bis (trichloromethyl) -s-triazine, 2,4, 6-tris (dibromomethyl) -s-triazine, 2,4, 6-tris (tribromomethyl) -s-triazine, 2-methyl-4, 6-bis (tribromomethyl) -s-triazine, 2-methoxy-4, 6-bis (tribromomethyl) -s-triazine, and the like.
As the photoacid generator, an organoborate compound can also be used. Specific examples of the organoborate compound include, for example, organoborates described in Japanese patent laid-open Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000 131837, 2002-107916, 2764769, 2000-310808, Kunz, Martin "Rad Tech'98. proceedings April19-22, 1998, Chicago" and the like, organoborates described in Japanese patent laid-open Nos. 6-157623, 6-175564, 6-175561, organoboron sulfonium complexes or organoboron oxonium complexes described in Japanese patent laid-open Nos. 6-175554, 6-175553, organoboron iodonium complexes described in Japanese patent laid-open No. 6-175553, and the like, And organoboron transition metal complex compounds such as organoboron phosphonium complexes described in Japanese patent application laid-open No. 9-188710, and organoboron transition metal complex compounds described in Japanese patent application laid-open Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014.
As the photoacid generator, a disulfone compound can also be applied. Examples of the disulfone compound include compounds described in Japanese patent application laid-open No. Sho 61-166544 and Japanese patent application laid-open No. 2001-132318, and diazodisulfone compounds.
Examples of the onium salt compound include diazonium salts described in s.i. schleisinger, photogr.sci.eng, 18, 387(1974), t.s.bal et al, Polymer, 21,423(1980), specifications of U.S. patent No. 4,069,055, ammonium salts described in japanese patent laid-open No. hei 4-365049, etc., phosphonium salts described in U.S. patent No. 4,069,055, specifications of U.S. patent No. 4,069,056, european patent No. 104,143, U.S. patent No. 339,049, specifications of U.S. patent No. 410,201, japanese patent laid-open No. 2-150848, iodine salts described in japanese patent laid-open No. hei 2-296514, european patent No. 370,693, european patent No. 390,214, european patent No. 233,567, european patent No. 297,443, european patent No. 297,442, U.S. patent No. 4,933,377, U.S. patent No. 161,811, U.S. 410,201, U.S. patent No. 339,049, U.S. Pat. 4,760,013, U.S. 36 2,833,827 8, 4,734,444, U.S. 36 2,833,827 8, and U.S. 4,734,444, Sulfonium salts described in specifications of german patent No. 2,904,626, german patent No. 3,604,580, and german patent No. 3,604,581, selenium salts described in j.v. crivello et al, Macromolecules, 10(6), 1307(1977), j.v. crivello et al, j.polymer sci, Polymer chem.ed., 17, 1047(1979), onium salts described in c.s.wen et al, Teh, proc.conf.rad.copper ASIA, p478 Tokyo, and arsenium salts, pyridinium salts described in Oct (1988), and the like.
As the onium salt, onium salts represented by the following general formulae (RI-I) to (RI-III) can be mentioned.
[ chemical formula 35]
Figure BDA0003775943360000541
In the formula (RI-I), Ar 11 The aryl group having 20 or less carbon atoms which may have 1 to 6 substituents is represented by the following general formula (I), and preferable substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamide groups having 1 to 12 carbon atoms or the likeArylamido, carbonyl, carboxyl, cyano, sulfonyl, thioalkyl having 1 to 12 carbon atoms, thioaryl having 1 to 12 carbon atoms. Z11 - The anion having a valence of 1 is a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion, and preferably perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, or sulfinate ion from the viewpoint of stability. In the formula (RI-II), Ar 21 、Ar 22 Each independently represents an aryl group having not more than 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 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 1 to 12 carbon atoms, an alkylamido or arylamido group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl 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 is a linear or branched member 21 - The anion having a valence of 1 is a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion, and preferably perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or carboxylate ion from the viewpoint of stability or reactivity. In the formula (RI-III), R 31 、R 32 、R 33 Each independently represents an aryl group having not more than 20 carbon atoms which may have 1 to 6 substituents, or an alkyl group, alkenyl group or alkynyl group, and preferably an aryl group in view of reactivity and stability. Preferred substituents include alkyl groups of 1 to 12 carbon atoms, alkenyl groups of 1 to 12 carbon atoms, alkynyl groups of 1 to 12 carbon atoms, aryl groups of 1 to 12 carbon atoms, alkoxy groups of 1 to 12 carbon atoms, aryloxy groups of 1 to 12 carbon atoms, halogen atoms, alkylamino groups of 1 to 12 carbon atoms, dialkylamino groups of 1 to 12 carbon atoms, C1 to C112 alkylamide or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z31 - The anion having a valence of 1 is a halide ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion from the viewpoint of stability or reactivity.
Specific examples thereof include the following.
[ chemical formula 36]
Figure BDA0003775943360000551
[ chemical formula 37]
Figure BDA0003775943360000561
[ chemical formula 38]
Figure BDA0003775943360000562
[ chemical formula 39]
Figure BDA0003775943360000571
When the photoacid generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 2 to 15% by mass, based on the total solid content of the composition of the present invention. The photoacid generator may contain only one kind, or may contain two or more kinds. When two or more types of photoacid generators are contained, the total amount thereof is preferably within the above range.
< thermal polymerization initiator >
The composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a compound having polymerizability. The addition of the thermal radical polymerization initiator enables the resin and the polymerizable compound to undergo a polymerization reaction in the heating step described later, and thus the solvent resistance can be further improved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the composition of the present invention. The thermal polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
< thermal acid generating agent >
The composition of the present invention may comprise a thermal acid generator.
The thermal acid generator has the following effects: the acid is generated by heating to promote a crosslinking reaction of at least one compound selected from the group consisting of a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound.
The thermal decomposition initiation temperature of the thermal acid generator is preferably 50 to 270 ℃, more preferably 50 to 250 ℃. Furthermore, it is preferable to select, as the thermal acid generator, a material which does not generate an acid when the composition is applied to a substrate and then dried (prebaking: about 70 to 140 ℃ C.), and generates an acid when the composition is subjected to final heating (curing: about 100 to 400 ℃ C.) after patterning in exposure and development, because a decrease in sensitivity during development can be suppressed.
The thermal decomposition initiation temperature was determined as the peak temperature of the lowest exothermic peak when the thermal acid generator was heated to 500 ℃ at 5 ℃/min in the pressure-resistant capsule.
Examples of the apparatus used for measuring the thermal decomposition initiation temperature include Q2000 (manufactured by TA Instruments).
The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and halogenated alkyl sulfonic acids such as trifluoromethanesulfonic acid. An example of such a thermal acid generator is the thermal acid generator described in paragraph 0055 of jp 2013-a 072935.
Among them, from the viewpoint of less residue in the organic membrane and less tendency to degrade the physical properties of the organic membrane, a thermal acid generator which generates an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms is more preferable, and as the thermal acid generator, a (4-hydroxyphenyl) dimethylsulfonium methanesulfonate, a (4- ((methoxycarbonyl) oxy) phenyl) dimethylsulfonium methanesulfonate, a benzyl (4-hydroxyphenyl) methyl sulfonium methanesulfonate, a benzyl (4- ((methoxycarbonyl) oxy) phenyl) methyl sulfonium methanesulfonate, a (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium methanesulfonate, a (4-hydroxyphenyl) dimethylsulfonium trifluoromethanesulfonate, a (4- ((methoxycarbonyl) oxy) phenyl) dimethyl sulfonium trifluoromethanesulfonate, a benzyl (4-hydroxyphenyl) methyl sulfonium trifluoromethanesulfonate, a (4-hydroxyphenyl) methyl sulfonium trifluoromethanesulfonate, Benzyl (4- ((methoxycarbonyl) oxy) phenyl) methylthioninium trifluoromethanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium trifluoromethanesulfonate, 3- (5- (((propylsulfonyl) oxy) imino) thiophen-2 (5H) -ylidene) -2- (o-tolyl) propionitrile, 2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane.
Further, the compound described in paragraph 0059 of Japanese patent application laid-open 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, and more preferably 0.1 part by mass or more, per 100 parts by mass of the specific resin. The content of 0.01 parts by mass or more promotes the crosslinking reaction, and thus the mechanical properties and solvent resistance of the organic film can be further improved. From the viewpoint of electrical insulation of the organic film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
< onium salt >
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
The kind of onium salt is not particularly limited, and preferable examples thereof include an ammonium salt, an Iminium salt, a sulfonium salt, an iodonium salt and a phosphonium salt.
Among these, ammonium salts or iminium salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, or phosphonium salts are preferable from the viewpoint of compatibility with the polymer.
The onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may be bonded to each other through a covalent bond or may not be bonded to each other through a covalent bond.
That is, the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or may be an intermolecular salt in which cation molecules and anion molecules, which are different molecules, are ionically bonded, but is preferably an intermolecular salt. In the curable resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded to each other by an ionic bond or may be dissociated from each other.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.
The onium salt used in the present invention may be a thermal alkali generator described later.
The thermal alkali generator is a compound which generates an alkali by heating, and examples thereof include a compound which generates an alkali when heated to 40 ℃ or higher.
[ ammonium salt ]
In the present invention, the ammonium salt means a salt of an ammonium cation with an anion.
Ammonium cation-
As ammonium cation, quaternary ammonium cations are preferred.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.
[ chemical formula 40]
Figure BDA0003775943360000601
In the formula (101), R 1 ～R 4 Each independently represents a hydrogen atom or a hydrocarbon group, R 1 ～R 4 At least 2 of which may be bonded to form a ring.
In the formula (101), R 1 ～R 4 Each independently is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R 1 ～R 4 Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like.
At R 1 ～R 4 In the case where at least 2 of the groups are bonded to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
The ammonium cation is preferably represented by any one of the following formulae (Y1-1) and (Y1-2).
[ chemical formula 41]
Figure BDA0003775943360000602
In the formulae (Y1-1) and (Y1-2), R 101 Represents an n-valent organic radical, R 1 And R in the formula (101) 1 Are as defined above, Ar 101 And Ar 102 Each independently represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R 101 Preferably a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon or a structure obtained by bonding these, more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or naphthalene n hydrogen atoms.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
In the formula (Y1-2), Ar 101 And Ar 102 Each independently is preferably phenyl or naphthyl, more preferably phenyl.
Anions-
The anion in the ammonium salt is preferably one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion, and the carboxylic acid anion is more preferably used for the purpose of achieving both the stability and the thermal decomposability of the salt. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylic acid anion.
The carboxylic acid anion is preferably an anion of a 2-valent or higher carboxylic acid having 2 or more carboxyl groups, and more preferably an anion of a 2-valent carboxylic acid. According to this embodiment, the stability, curability, and developability of the curable resin composition can be further improved. In particular, the use of the anion of the 2-valent carboxylic acid can further improve the stability, curability, and developability of the curable resin composition.
The carboxylic acid anion is preferably represented by the following formula (X1).
[ chemical formula 42]
Figure BDA0003775943360000611
In the formula (X1), EWG represents an electron withdrawing group.
In the present embodiment, the electron-withdrawing group represents a group in which the hammett substituent constant σ m shows a positive value. Sigma is described in Duchang, journal of the society of organic synthetic chemistry, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
As an example of a substituent in which σ m shows a positive value, CF can be given 3 Base (. sigma.m.0.43), CF 3 C (═ O) group (σ m ═ 0.63), HC ≡ C group (σ m ═ 0.21), CH ≡ C group 2 CH (σ m) group (0.06), Ac (σ m) group (0.38), MeOC (O) group (σ m) group (0.37), MeC (c) (O)O) CH ═ CH group (σ m ═ 0.21), PhC (═ O) group (σ m ═ 0.34), H 2 NC(＝O)CH 2 And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).
The EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).
[ chemical formula 43]
Figure BDA0003775943360000621
In the formulae (EWG-1) to (EWG-6), R x1 ～R x3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.
In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).
[ chemical formula 44]
Figure BDA0003775943360000622
In the formula (XA), L 10 Represents a single bond or is selected from alkylene, alkenylene, aromatic group, -NR X A 2-valent linking group in a combination of these, R X Represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion.
From the viewpoint of facilitating cyclization of the heterocyclic polymer-containing precursor at low temperature and facilitating improvement of storage stability of the curable resin composition, the onium salt in the present invention preferably contains an ammonium cation as a cation, and the onium salt preferably contains an anion having a pka (pkah) of a conjugate acid of 2.5 or less as an anion, and more preferably contains an anion of 1.8 or less.
The lower limit of the pKa is not particularly limited, but is preferably-3 or more, more preferably-2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the precursor containing the heterocyclic polymer or the like becomes good.
As the pKa, reference can be made to the values described in the Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O.A., Nachod, F.C., eds.; compiled: Braude, E.A., Nachod, F.C., Academic Press, New York,1955) or Data for Biochemical Research (authors: Danws, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) were used.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these.
[ chemical formula 45]
Figure BDA0003775943360000631
[ Ammonilinium salt ]
In the present invention, the iminium salt means a salt of an iminium cation with an anion. The anion may be the same anion as in the above ammonium salt, and the preferred embodiment is the same.
Ammonium sulfite cation-
As the iminium cation, a pyridinium cation is preferable.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.
[ chemical formula 46]
Figure BDA0003775943360000641
In the formula (102), R 5 And R 6 Each independently represents a hydrogen atom or a hydrocarbon group, R 7 Represents a hydrocarbon group, R 5 ～R 7 At least 2 of which may be bonded to form a ring.
In the formula (102), R 5 And R 6 And R in the above formula (101) 1 ～R 4 Have the same meaning, preferred modeThe same applies.
In the formula (102), R 7 Preferably with R 5 And R 6 At least 1 of which is bonded to form a ring. The above rings may contain heteroatoms. Examples of the hetero atom include a nitrogen atom. The ring is preferably a pyridine ring.
The iminium cation is preferably represented by any one of the following formulae (Y1-3) to (Y1-5).
[ chemical formula 47]
Figure BDA0003775943360000642
In the formulae (Y1-3) to (Y1-5), R 101 Represents an n-valent organic radical, R 5 And R in the formula (102) 5 Are as defined above, R 7 And R in the formula (102) 7 The same as above, and n and m are integers of 1 or more.
In the formula (Y1-3), R 101 Preferably, the aliphatic hydrocarbon, aromatic hydrocarbon or a bonded structure thereof is a group obtained by removing n hydrogen atoms, more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and still more preferably 1.
Specific examples of the iminium salt include the following compounds, but the present invention is not limited to these.
[ chemical formula 48]
Figure BDA0003775943360000651
[ sulfonium salt ]
In the present invention, sulfonium salt means a salt of a sulfonium cation with an anion. The anion may be the same anion as in the above-mentioned ammonium salt, and the preferable embodiment is also the same.
Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
The sulfonium cation is preferably a cation represented by the following formula (103).
[ chemical formula 49]
Figure BDA0003775943360000652
In the formula (103), R 8 ～R 10 Each independently represents a hydrocarbon group.
R 8 ～R 10 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R 8 ～R 10 Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 8 ～R 10 The groups may be the same or different, but from the viewpoint of synthetic compatibility, the same groups are preferred.
Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 50]
Figure BDA0003775943360000661
[ iodized salt ]
In the present invention, iodonium salt means a salt of iodonium cation with anion. The anion may be the same anion as in the above ammonium salt, and the preferred embodiment is the same.
Iodine cation-
As the iodonium cation, a diaryliodonium cation is preferable.
Further, the iodonium cation is preferably a cation represented by the following formula (104).
[ chemical formula 51]
Figure BDA0003775943360000671
In the formula (104), R 11 And R 12 Each independently represents a hydrocarbon group.
R 11 And R 12 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R 11 And R 12 Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 11 And R 12 The groups may be the same or different, but from the viewpoint of synthetic compatibility, the same groups are preferable.
Specific examples of the iodide salt include the following compounds, but the present invention is not limited to these.
[ chemical formula 52]
Figure BDA0003775943360000681
[ phosphonium salt ]
In the present invention, phosphonium salts mean salts of phosphonium cations with anions. The anion may be the same anion as in the above-mentioned ammonium salt, and the preferable embodiment is also the same.
Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include a tetraalkylphosphonium cation, a triarylmonoalkylphosphonium cation and the like.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
[ chemical formula 53]
Figure BDA0003775943360000682
In the formula (105), R 13 ～R 16 Each independently represents a hydrogen atom or a hydrocarbon group.
R 13 ～R 16 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R 13 ～R 16 Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 13 ～R 16 The groups may be the same or different, but from the viewpoint of synthetic compatibility, the same groups are preferable.
Specific examples of the phosphonium salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 54]
Figure BDA0003775943360000691
When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
One or two or more kinds of onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.
< thermal alkali production agent >
The curable resin composition of the present invention may further contain a thermal alkali generator.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains a thermal alkali generator.
The other thermal alkali-generating agent may be a compound corresponding to the onium salt, or may be a thermal alkali-generating agent other than the onium salt.
Examples of the thermal alkali-generating agent other than the onium salt include nonionic thermal alkali-generating agents.
Examples of the nonionic thermoalcogenating agent include compounds represented by the formula (B1) and (B2).
[ chemical formula 55]
Figure BDA0003775943360000701
In the formulae (B1) and (B2), Rb 1 、Rb 2 And Rb 3 Each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 And Rb 2 Not both as hydrogen atoms. And, Rb 1 、Rb 2 And Rb 3 Not all have a carboxyl group. In the present specification, the tertiary amine structure means a nitrogen atom having a valence of 3And 3 of the above-mentioned bonds are all covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the carbon atom to be bonded is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, the carbon atom is not limited thereto.
In the formulae (B1) and (B2), Rb represents 1 、Rb 2 And Rb 3 Preferably at least 1 of these comprises a cyclic structure, more preferably at least 2 comprise a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which 2 monocyclic rings are condensed. Monocyclic rings are preferably 5-membered rings or 6-membered rings, preferably 6-membered rings. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
More specifically, Rb 1 And Rb 2 Preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). These groups may have a substituent in a range in which the effect of the present invention is exerted. Rb 1 And Rb 2 May be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. Rb 1 And Rb 2 Particularly preferred is a linear, branched or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), more preferred is a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), and further preferred is a cyclohexyl group which may have a substituent.
As Rb 3 Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, further preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, further preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, further preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, further preferably 8 to 20 carbon atoms, further preferably 8 to 8 amino groups) 16) An alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, further preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms) or an arylalkoxy group (preferably having 7 to 23 carbon atoms, further preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). Among them, preferred are cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups. Rb 3 The compound may have a substituent within a range in which the effects of the present invention are exhibited.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ chemical formula 56]
Figure BDA0003775943360000711
In the formula, Rb 11 And Rb 12 And Rb 31 And Rb 32 Respectively with Rb in formula (B1) 1 And Rb 2 The same is true.
Rb 13 The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms) may have a substituent within a range in which the effects of the present invention are exhibited. Wherein, Rb is 13 Arylalkyl is preferred.
Rb 33 And Rb 34 Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), and preferably a hydrogen atom.
Rb 35 Is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms) or an alkenyl group(preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and preferably an aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 57]
Figure BDA0003775943360000721
Rb 11 And Rb 12 And Rb in the formula (B1-1) 11 And Rb 12 Have the same meaning.
Rb 15 And Rb 16 The alkyl group is preferably a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 12, more preferably 1 to 6, further preferably 1 to 3), an alkenyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, further preferably 2 to 3), an aryl group (preferably a carbon number of 6 to 22, more preferably 6 to 18, further preferably 6 to 10), an arylalkyl group (preferably a carbon number of 7 to 23, more preferably 7 to 19, further preferably 7 to 11), preferably a hydrogen atom or a methyl group.
Rb 17 Preferably an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and among them, an aryl group is preferable.
The molecular weight of the nonionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.
Specific examples of the compound as the thermal alkali-producing agent in the onium salt or specific examples of the thermal alkali-producing agent other than the onium salt include the following compounds.
[ chemical formula 58]
Figure BDA0003775943360000731
[ chemical formula 59]
Figure BDA0003775943360000741
[ chemical formula 60]
Figure BDA0003775943360000751
The content of the other thermoalcogenating agent is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One or more than two kinds of the thermal alkali-producing agents can be used. When two or more kinds are used, the total amount is preferably within the above range.
< crosslinking agent >
The curable resin composition of the present invention preferably contains a crosslinking agent.
Examples of the crosslinking agent include a radical crosslinking agent and other crosslinking agents.
< radical crosslinking agent >
The curable resin composition of the present invention preferably further comprises a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. 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, and a (meth) acryloyl group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, and from the viewpoint of reactivity, a (meth) acryloyloxy group is more preferable.
The radical crosslinking agent may be a compound having 1 or more ethylenically unsaturated bonds, and more preferably a compound having 2 or more ethylenically unsaturated bonds.
The compound having 2 ethylenically unsaturated bonds is preferably a compound having 2 ethylenically unsaturated bond-containing groups described above.
Further, the curable resin composition of the present invention preferably contains a compound having 3 or more ethylenically unsaturated bonds as a radical crosslinking agent from the viewpoint of the film strength of the obtained pattern (cured film). The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 3 to 6 ethylenically unsaturated bonds.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound having 3 to 15, still more preferably a compound having 3 to 10, and particularly preferably a compound having 3 to 6.
On the other hand, the radical crosslinking agent is particularly preferably the above-mentioned compound having 2 ethylenically unsaturated bonds from the viewpoint of developability.
Also, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having 2 ethylenically unsaturated bonds and the above-mentioned compound having 3 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 further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, or the like can also be preferably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having dissociative substituent groups such as halo groups (halogen groups) or p-toluenesulfonyloxy groups (tosyloxy groups) and monofunctional or polyfunctional alcohols, amines, thiols are preferable. As another example, a compound group such as unsaturated phosphonic acid, styrene or other styrene derivative, vinyl ether, allyl ether, or the like may be used instead of the unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein.
Further, the radical crosslinking agent is also preferably a compound having a boiling point of 100 ℃ or higher at normal pressure. Examples thereof include compounds obtained by (meth) acrylating polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane or other polyfunctional alcohols, urethane (meth) acrylates as described in Japanese patent publication No. 48-041708, Japanese patent publication No. 50-006034, Japanese patent publication No. 51-037193, and the like, The polyester acrylate described in each of Japanese patent application laid-open Nos. Sho 48-064183, Sho 49-043191 and Sho 52-030490, and a polyfunctional acrylate or methacrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (meth) acrylic acid, and a mixture thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there may be mentioned a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid.
Further, as a preferable radical crosslinking agent other than the above, compounds having a fluorene ring and having 2 or more ethylenically unsaturated bond-containing groups or cardo (cardo) resins described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like can be used.
Further, as another example, there may be mentioned a specific unsaturated compound described in Japanese patent publication No. 46-043946, Japanese patent publication No. 01-040337, and Japanese patent publication No. 01-040336, a vinylphosphonic acid-based compound described in Japanese patent publication No. 02-025493, and the like. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photopolymerizable monomers and oligomers in journal of vol.20, No.7, pages 300 to 308 (1984) of the Japan adhesive Association can also be used.
In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219 may be preferably used, and these contents are incorporated in the present specification.
Further, a compound obtained by (meth) acrylating ethylene oxide or propylene oxide added to a polyfunctional alcohol, which is described as a specific example of the formula (1) and the formula (2) in jp-a-10-062986, can also be used as a radical crosslinking agent.
Further, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical crosslinking agents, and these contents are incorporated in the present specification.
As the radical crosslinking agent, dipentaerythritol triacrylate (KAYARAD-330 as a commercially available product; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (KAYARAD-320 as a commercially available product; Nippon Kayaku Co., manufactured by Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD-310 as a commercially available product; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercially available product; Nippon Kakuu Co., manufactured by Ltd., manufactured by A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.) and structures in which (meth) acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues are preferable. Oligomeric forms of these can also be used.
Commercially available products as the radical crosslinking agent include, for example, SR-494 (manufactured by Sartomer Company, Inc.) as a 4-functional acrylate having 4 vinyloxy chains, SR-209, 231, 239, Nippon Kayaku Co., Ltd., DPCA-60 (manufactured by Ltd.) as a 6-functional acrylate having 6 oxypentyl chains, TPA-330 (manufactured by Ltd.) as a 3-functional acrylate having 3 isobutenoxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakara Co., Ltd., manufactured by Lppon Chemical Co., Ltd.), NK Ester M-40G, NK Ester M-9300, NK Ester HA-40H (manufactured by Kaklu Co., Ltd., HA, Kayaku Co., Ltd.), and HA-40H (manufactured by Kayaku Co., Ltd.), ltd, manufactured), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical co., ltd., manufactured), BLEMMER PME400 (manufactured by NOF CORPORATION), and the like.
As the radical crosslinking agent, urethane acrylates described in JP-B-48-041708, JP-B-51-037193, JP-B-02-032293 and JP-B-02-016765, urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.
The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl 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 having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. In particular, it is preferable that the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol in the radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Examples of commercially available products include polybasic acid-modified acrylic acid oligomers produced by TOAGOSEI CO., LTD., M-510, M-520, and the like.
The radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the workability in production is excellent, and the developability is excellent. Further, the polymerizability is good. On the other hand, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300mgKOH/g, and particularly preferably 1 to 100mgKOH/g, from the viewpoint of the developing speed in the alkali development. The acid value is determined in accordance with JIS K0070: 1992 for the determination.
From the viewpoint of pattern resolution and film stretchability, the curable resin composition of the present invention preferably uses a 2-functional methacrylate or acrylate.
Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200), 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 dimethacrylate, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, and mixtures thereof, Bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid modified dimethacrylate, 2-functional acrylate having another urethane bond, and 2-functional methacrylate having a urethane bond. These may be used in combination of two or more kinds as necessary.
In addition, examples of the radical crosslinking agent having 2 or more functions include diallyl phthalate, triallyl trimellitate, and the like.
From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As monofunctional radical crosslinking agents, 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, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional radical crosslinking agent is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.
When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.
The radical crosslinking agent may be used alone, but two or more kinds may be used in combination. When two or more kinds are used simultaneously, the total amount is preferably within the above range.
< other crosslinking Agents >
The curable resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent.
In the present invention, the other crosslinking agent is a crosslinking agent other than the radical crosslinking agent, preferably a compound having in the molecule a plurality of groups which promote a reaction of forming a covalent bond with other compounds in the composition or a reaction product thereof by the photosensitization of the photosensitizer, preferably a compound having in the molecule a plurality of groups which promote a reaction of forming a covalent bond with other compounds in the composition or a reaction product thereof by the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photosensitizer in an exposure process.
The other crosslinking agent is preferably a compound having at least one group selected from a hydroxymethyl group and an alkoxymethyl group, and more preferably a compound having a structure in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to a nitrogen atom.
Examples of the other crosslinking agent include compounds having a structure in which a hydrogen atom of an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group by reacting formaldehyde or formaldehyde and an alcohol with an amino group-containing compound such as melamine, glycoluril, urea, an alkyleneurea, or benzoguanamine. The method for producing these compounds is not particularly limited as long as the compounds have the same structure as the compounds produced by the above-described method. Further, the methylol groups of these compounds may be self-condensed with each other to form an oligomer.
A crosslinking agent using melamine as the amino group-containing compound is referred to as a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea, or alkyleneurea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkyleneurea is referred to as an alkyleneurea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from a urea-based crosslinking agent and a melamine-based crosslinking agent, and more preferably contains at least one compound selected from a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described later.
Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.
Specific examples of the urea-based crosslinking agent include a glycoluril-based crosslinking agent such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethyl glycoluril, dipropoxymethyl glycoluril, tripropoxymethyl glycoluril, tetrapropoxymethyl glycoluril, monobutyloxymethylated glycoluril, dibutoxymethyl glycoluril, tributoxymethyl glycoluril or tetrabutoxymethylated glycoluril;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea and bisbutoxymethylurea;
ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylmethylated ethylene urea, dipropoxymethylmethylated ethylene urea, monobutyloxymethylated ethylene urea or dibutoxymethylated ethylene urea;
propylene urea-based crosslinking agents such as monohydroxymethylated propyleneurea, dihydroxymethylated propyleneurea, monomethoxymethylated propyleneurea, dimethoxymethylated propyleneurea, monoethoxymethylated propyleneurea, diethoxymethyl propyleneurea, monopropoxymethyl propyleneurea, dipropoxymethyl propyleneurea, monobutyloxymethylated propyleneurea, or dibutoxymethyl propyleneurea;
1, 3-bis (methoxymethyl) 4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.
Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, and dimethoxymethylated benzoguanamine, trimethoxy methylated benzoguanamine, tetraethoxy methylated benzoguanamine, monopropoxy methylated benzoguanamine, dipropoxy methylated benzoguanamine, tripropoxy methylated benzoguanamine, tetrapropoxy methylated benzoguanamine, monobutyloxymethylbenzoguanamine, dibutoxymethyl benzoguanamine, tributoxymethyl benzoguanamine, tetrabutoxy methylated benzoguanamine, and the like.
In addition, as the compound having at least one group selected from a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) may be preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxybenzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl benzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4 ', 4 "-ethylidenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3 ', 5, 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.
As other crosslinking agents, commercially available products may be used, and preferable commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), 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-BPF, TML-BPE, TML-BPA, TML-BPAP, TML-TMBP-TML-P, TriML-35XL, TML-HQ, TML-BPE, TML-BPA, TMBPAP, TMBPOM-PP, TMBPE, TMBPM-BPE, TMBPA, TMBPE, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, made by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (above, made by Sanwa Chemical Co., Ltd.), and the like.
The curable resin composition of the present invention also preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.
[ epoxy Compound (Compound having epoxy group) ]
The epoxy compound is preferably a compound having 2 or more epoxy groups in 1 molecule. The epoxy group undergoes a crosslinking reaction at 200 ℃ or lower, and a dehydration reaction due to crosslinking does not occur, so that film shrinkage is less likely to occur. Therefore, the epoxy compound is effective for curing at low temperature and suppressing warpage of the curable resin composition.
The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group represents a group having a repeating unit of ethylene oxide of 2 or more, and preferably has a repeating unit number of 2 to 15.
Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the epoxy group-containing silicones 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-81665, EPICLON (registered trademark) EXA-81660, EPICLON (registered trademark) EXA-8169, EPICLON-81660, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (trade name, manufactured by DIC Corporation, supra), Rika 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 Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA CORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOXE (registered trademark) GT400, EPOXD (registered trademark) GT401, EPOXE (registered trademark) PB4700, LEAD (registered trademark) CELPB 0, NUS (registered trademark) 0134, DaL Corporation (registered trademark) NC-3000, NC-NC 3 NC-3000, and NC 1 NC), 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, trade name, Nippon Kayaku Co., Ltd., manufactured by Ltd.), and the like.
[ Oxetane compound (compound having an oxetanyl group) ]
Examples of the oxetane compound include a compound having 2 or more oxetane rings in 1 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. Specifically, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.
[ benzoxazine compound (compound having benzoxazolyl group) ]
The benzoxazine compound does not generate outgassing upon curing due to a crosslinking reaction from a ring-opening addition reaction, and further reduces thermal shrinkage to suppress generation of warpage, and is therefore preferable.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine, P-d type benzoxazine, F-a type benzoxazine (hereinafter, referred to as trade name, manufactured by SHIKOKU CHEMICALS CORPORATION), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.
The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the curable resin composition of the present invention. The other crosslinking agent may contain only one kind, or may contain two or more kinds. When two or more other crosslinking agents are contained, the total amount thereof is preferably within the above range.
< Compounds having a sulfonamide Structure, Compounds having a Thiourea Structure >
From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the curable resin composition of the present invention preferably further contains at least one compound selected from a compound having a sulfonamide structure and a compound having a thiourea structure.
[ Compound having a sulfonamide Structure ]
The sulfonamide structure is represented by the following formula (S-1).
[ chemical formula 61]
Figure BDA0003775943360000851
In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and each independently represents a bonding position to another structure.
The above-mentioned R is preferably the same as R in the following formula (S-2) 2 The same groups.
The compound having a sulfonamide structure may be a compound having 2 or more sulfonamide structures, but is preferably a compound having 1 sulfonamide structure.
The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
[ chemical formula 62]
Figure BDA0003775943360000852
In the formula (S-2), R 1 、R 2 And R 3 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 、R 2 And R 3 2 or more of them may be bonded to each other to form a ring structure.
R 1 、R 2 And R 3 Each independently preferably is a 1-valent organic group.
As R 1 、R 2 And R 3 Examples of (3) include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, and a heterocycleAnd a group obtained by combining 2 or more of these groups.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the heterocyclic group include groups obtained by removing 1 hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyranyl ring, or a triazine ring.
Among them, R is preferred 1 Is aryl and R 2 And R 3 Each independently a hydrogen atom or an alkyl group.
Examples of the compound having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N-dimethylmethanesulfonamide, N-dimethylethanesulfonamide, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethylsulfonamide and the like.
[ Compound having a Thiourea Structure ]
The thiourea structure is represented by the following formula (T-1).
[ chemical formula 63]
Figure BDA0003775943360000871
In the formula (T-1), R 4 And R 5 Each independently represents a hydrogen atom or a 1-valent organic group, R 4 And R 5 May be bonded to form a ring structure, R 4 May be bonded to other structures bonded to form a ring structure, R 5 May be bonded to other structures to form ring structures, each independently representing a bonding site to the other structure.
R 4 And R 5 Each independently preferably a hydrogen atom.
As R 4 And R 5 Examples of (3) include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a combination of 2 or more of these, and the like.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the heterocyclic group include groups obtained by removing 1 hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyranyl ring, or a triazine ring.
The compound having a thiourea structure may be a compound having 2 or more thiourea structures, but is preferably a compound having 1 thiourea structure.
The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
[ chemical formula 64]
Figure BDA0003775943360000881
In the formula (T-2), R 4 ～R 7 Each independently represents a hydrogen atom or a 1-valent organic group, R 4 ～R 7 At least 2 of which may be bonded to each other to form a ring structure.
In the formula (T-2), R 4 And R 5 And R in the formula (T-1) 4 And R 5 The same applies to the preferred embodiments.
In the formula (T-2), R 6 And R 7 Each independently is preferably a 1-valent organic group.
In the formula (T-2), R 6 And R 7 Preferred mode of the 1-valent organic group in (1) is the same as R in the formula (T-1) 4 And R 5 The preferable mode of the 1-valent organic group in (1) is the same.
Examples of the compound having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N '- (2-hydroxyethyl) thiourea, 1-adamantylthiourea, N-benzoylthiourea, N' -diphenylthiourea, 1-benzyl-phenylthiourea, 1, 3-dibutylthiourea, 1, 3-diisopropylthiourea, 1, 3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiothiourea, trimethylthiourea, tetramethylthiourea, N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), Carbimazole (Carbimazole), 1, 3-dimethyl-2-thiohydantoin, and the like.
[ content ]
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.2 to 3% by mass, based on the total mass of the curable resin composition of the present invention.
The curable resin composition of the present invention may contain only one compound selected from compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more compounds. In the case where only one is contained, the content of the compound is preferably within the above range, and in the case where two or more are contained, the total amount thereof is preferably within the above range.
< migration inhibitor >
The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, migration of metal ions from the metal layer (metal wiring) into the curable resin composition layer can be effectively inhibited.
The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole 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, 6H-pyran ring, and triazine ring), compounds having a thiourea and a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole, benzotriazole, 5-methylbenzotriazole, 3-amino-1, 2, 4-triazole, and 3, 5-diamino-1, 2, 4-triazole, tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole, and purine-based compounds such as purine, adenine, and guanine can be preferably used.
Among these, a mode in which the curable resin composition of the present invention further contains at least one compound selected from the group consisting of 5-methylbenzotriazole, 3-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole and 5-amino-1H-tetrazole as a migration inhibitor is also one of preferred modes of the present invention.
From the viewpoint of improving the adhesion to metal wiring, the curable resin composition of the present invention preferably contains a compound having an amino group as a migration inhibitor, more preferably contains a compound having a heterocyclic ring and an amino group, further preferably contains a compound having one or more heterocyclic rings selected from an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring and a triazine ring, and particularly preferably contains an azole compound having an amino group, and most preferably contains a triazole compound having an amino group or a tetrazole compound having an amino group.
Alternatively, an ion scavenger that scavenges anions such as halide ions can also be used.
As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent laid-open publication No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent laid-open publication No. 2009-283711, compounds described in paragraph 0052 of Japanese patent laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent laid-open publication No. 2012-194520, compounds described in paragraph 0166 of International publication No. 2015/199219, and the like.
Specific examples of the migration inhibitor include the following compounds.
[ chemical formula 65]
Figure BDA0003775943360000901
When the curable resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the curable resin composition.
The migration inhibitor may be one kind only, or two or more kinds. When the number of migration inhibitors is two or more, the total amount thereof is preferably within the above range.
< polymerization inhibitor >
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 ' -thiobis (3-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerous salt, 2 ' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, p-butylphenol, 1,4 ' -thiobis (3-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, ethylene diamine, and the like, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane, 1,3, 5-tris (4-tert-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 radical, N-nitroso-N-methyl-1-naphthol, N-nitroso-phenyl-1-naphthol, N-nitroso-methyl-1-naphthol, N-methyl-4-hydroxy-3, 5-dimethylbenzyl-triazine-2, 4,6, 6-tetramethylpiperidine 1-oxyl radical, and mixtures thereof, Phenothiazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, 2,6, 6-tetramethylpiperidine 1-oxyl, phenoxazine, and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used.
The following compound (Me is methyl) can be used.
[ chemical formula 66]
Figure BDA0003775943360000911
When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is, for example, 0.01 to 20.0% by mass, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the curable resin composition of the present invention. When the storage stability of the curable resin composition solution is required, the storage stability is preferably 0.02 to 15.0 mass%, and in this case, more preferably 0.05 to 10.0 mass%.
The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is two or more, the total amount thereof is preferably within the above range.
< modifier for improving adhesion of Metal >
The curable resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent, an aluminum-based adhesion improver, a titanium-based adhesion improver, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β keto ester (β keto ester) compound, and an amino compound.
Among these, the curable resin composition of the present invention preferably contains a silane coupling agent, an aluminum-based adhesive auxiliary agent, a titanium-based adhesive auxiliary agent, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -keto ester compound, an amino compound, and the like.
Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and a compound described in paragraph 0055 of International publication No. 2014/097594. Further, as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.
[ chemical formula 67]
Figure BDA0003775943360000921
Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-hydroxyethoxysilane, N-hydroxyethoxypropyltrimethoxysilane, N-hydroxyethoxypropylmethyldimethoxysilane, N-hydroxyethoxypropyltrimethoxysilane, N-hydroxyethoxypropylmethyldimethoxysilane, N-hydroxyethoxysilane, N-hydroxyethoxypropyltrimethoxysilane, N-3-hydroxyethoxypropyltrimethoxysilane, p-hydroxyethoxysilane, p-hydroxysilane, p-hydroxysilane, p-hydroxysilane, p-2-hydroxysilane, p-p, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of jp 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of jp 2013-072935 can be used.
[ aluminum-based adhesion promoter ]
Examples of the aluminum-based adhesion promoter include tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, and aluminum ethylacetoacetate diisopropoxide.
The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. When the lower limit is not less than the above-mentioned lower limit, the adhesion between the pattern and the metal layer becomes good, and when the upper limit is not more than the above-mentioned upper limit, the heat resistance and the mechanical properties of the pattern become good. The metal adhesion improver may be one kind only, or two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.
< modifier for improving adhesion of Metal >
The curable resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935 can be used.
The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the heterocycle-containing polymer precursor. When the lower limit value is not less than the lower limit value, the adhesion between the cured film after the curing step and the metal layer becomes good, and when the upper limit value is not more than the upper limit value, the heat resistance and the mechanical properties of the cured film after the curing step become good. The metal adhesion improver may be one kind only, or two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.
< other additives >
The curable resin composition of the present invention may contain various additives, for example, a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, and the like, as necessary within the range in which the effects of the present invention can be obtained. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the curable resin composition.
[ sensitizer ]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs a specific active radiation to become an electron excited state. The sensitizer in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like to produce effects such as electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are decomposed by chemical change, and radicals, acids, or bases are generated.
For example, compounds such as ethanolamine-based, benzophenone-based, michler's ketone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyrrolidone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds can be used.
Examples of the sensitizer include Michler's ketone, 4 ' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 ' -bis (dimethylamino) chalcone, 4 ' -bis (diethylamino) chalcone, p-dimethylaminobenylidenylindanone, p-dimethylaminobenzylidenediindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) propanone, 1, 3-bis (4' -diethylaminobenzylidene) propanone, 3 '-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, N-tolyldiethanolamine, N-tolylethanolamine, N-methylketoprofen, N-methyltestosterone, N-methylethanolamine, L-methylketol, L-methylethanolamine, L-methylenol, L-C-L-, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminostyryl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3 ', 4' -dimethylacetanilide, and the like.
As the sensitizer, a sensitizing dye may also be used.
The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, relative to the total solid content of the curable resin composition of the present invention. One sensitizer may be used alone, or two or more sensitizers may be used simultaneously.
[ chain transfer agent ]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of the third edition of the polymer dictionary (edited by the society of macromolecules, 2005). As the chain transfer agent, for example, those having-S-, -SO-in the molecule can be used 2 The group of-S-, -N-O-, SH, PH, SiH, and GeH, dithiobenzoate having thionylthio group for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, trithiocarbonate, dithiocarbamate, Xanthate (Xanthate) compounds, and the like. These are capable of supplying hydrogen to a low-activity radical to generate a radical, or generating a radical by deprotonation after oxidation. In particular, a thiol compound can be preferably used.
Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International publication No. 2015/199219 can be used.
When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be one kind alone, or two or more kinds thereof. When the number of the chain transfer agents is two or more, the total amount thereof is preferably within the above range.
[ surfactant ]
From the viewpoint of further improving coatability, various types of surfactants may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Also, the following surfactants are also preferable. In the following formulae, the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.
[ chemical formula 68]
Figure BDA0003775943360000951
Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese patent application laid-open No. 2010-164965, the contents of which are incorporated herein by reference. Further, examples of commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.
The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving properties, and has good solubility in the composition.
Examples of the Silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc., above), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH, above).
Examples of the hydrocarbon-based surfactant include PIONIN A-76, New Kalgen 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-P, and PIONIN P-4050-T (these are Takemoto Oil & Fat, manufactured by Ltd1028.).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available products include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-356315 (manufactured by TAKEMOTO L & FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical co., LTD.), and the like.
Specific examples of the cationic surfactant include organosiloxane polymer KP341(Shin-Etsu Chemical co., ltd.), (meth) acrylic (co) polymer Polyflow nos. 75, 77, 90, 95(Kyoeisha Chemical co., ltd.), W001(Yusho co., ltd.), and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho co., ltd.), SANDET BL (manufactured by SANYO KASEI co., ltd.), and the like.
When the curable resin composition of the present invention contains a surfactant, 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 curable resin composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total amount thereof is preferably within the above range.
[ higher fatty acid derivatives ]
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the curable resin composition of the present invention so as to be unevenly distributed on the surface of the curable resin composition during drying after coating.
Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of international publication No. 2015/199219 can be used.
When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be one kind or two or more kinds. When the number of the higher fatty acid derivatives is two or more, the total amount thereof is preferably within the above range.
[ inorganic particles ]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. mu.m, more preferably 0.02 to 1.5. mu.m, still more preferably 0.03 to 1.0. mu.m, and particularly preferably 0.04 to 0.5. mu.m.
When the average particle diameter of the inorganic particles is contained in a large amount, the mechanical properties of the cured film may be deteriorated. When the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may be reduced by scattering of the exposure light.
[ ultraviolet light absorber ]
The compositions of the present invention may comprise an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ones can be used.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like, and examples of the benzophenone-based ultraviolet absorber include 2,2 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and the like. Examples of the benzotriazole-based ultraviolet absorber 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, and, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- [2 ' -hydroxy-5 ' - (1,1,3, 3-tetramethyl) phenyl ] benzotriazole and the like.
Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Further, as examples of the triazine-based ultraviolet absorber, examples thereof include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine and the like; tris (hydroxyphenyl) triazine compounds such as 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-hydroxypropoxy) phenyl ] -1,3, 5-triazine, and the like.
In the present invention, the above-mentioned various ultraviolet absorbers may be used singly or in combination of two or more.
The composition of the present invention may contain an ultraviolet absorber or not, but in the case of containing an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, relative to the total solid content mass of the composition of the present invention.
[ 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 the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown in the following I) to VII):
I) titanium chelate compounds: among them, a titanium chelate compound having 2 or more alkoxy groups is more preferable from the viewpoint that the negative photosensitive resin composition has good storage stability and can obtain a good cured pattern. Specific examples thereof include bis (triethanolamine) diisopropoxytitanium, bis (2, 4-glutarate di (n-butoxy) titanium, bis (2, 4-glutarate) diisopropoxytitanium, bis (tetramethylheptanedionate) diisopropoxytitanium, bis (ethylacetoacetate) diisopropoxytitanium, and the like.
II) titanium tetraalkoxide compound: examples thereof include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexoxy) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearoyloxy titanium, and tetra [ bis {2,2- (allyloxymethyl) butoxy } ] titanium.
III) titanocene compound: examples thereof include pentamethylcyclopentadienyltrimethylenetitanium, bis (. eta.5-2, 4-cyclopentadien-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. eta.5-2, 4-cyclopentadien-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
IV) a monoalkoxytitanium compound: examples thereof include titanium tris (dioctylphosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.
V) titanium oxide compound: examples thereof include bis (glutarate) titanium oxide, bis (tetramethylpimelate) titanium oxide, and phthalocyanine titanium oxide.
VI) titanium tetraacetylacetonate compound: such as titanium tetraacetylacetonate.
VII) titanate coupling agent: for example, isopropyl tris (dodecyl) benzenesulfonyl titanate and the like.
Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound and III) titanocene compound, from the viewpoint of exerting more excellent chemical resistance. In particular, bis (ethylacetoacetate) diisopropoxytitanium, tetrakis (n-butoxy) titanium and bis (. eta.5-2, 4-cyclopentadien-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium are preferred.
When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained cured pattern, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.
[ antioxidant ]
The composition of the present invention may comprise an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol antioxidant can be used. Preferable examples of the phenol compound include hindered phenol compounds. Preferred are compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can be preferably used. Examples of the phosphorus-based antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphorinane-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4,6,9, 11-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphorinane-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-tert-butyl-6-methylphenol) phosphite. Examples of commercially available antioxidants include ADKSTAAO-20, ADKSTAAO-30, ADKSTATAAO-40, ADKSTAAO-50F, ADKSTAAO-60G, ADKSTAAO-80, and ADKSTAAO-330 (manufactured by ADEKA CORPORATION). Further, as the antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese patent No. 6268967 can be used. Also, the composition of the present invention may contain a latent antioxidant as needed. Examples of the potential antioxidant include compounds in which a site that functions as an antioxidant is protected with a protecting group, and compounds in which the protecting group is released by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst to function as an antioxidant. Examples of the potential antioxidant include compounds described in International publication Nos. 2014/021023, 2017/030005 and 2017-008219. Examples of commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. Preferable examples of the antioxidant include 2, 2-thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butylphenol, and a compound represented by the general formula (3).
[ chemical formula 69]
Figure BDA0003775943360001011
In the general formula (3), R 5 Represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R 6 Represents an alkylene group having 2 or more carbon atoms. R 7 An alkylene group having 2 or more carbon atoms, and an organic group having a valence of 1 to 4 and containing at least one of an O atom and an N atom. k represents an integer of 1 to 4.
The compound represented by the general formula (3) suppresses oxidative deterioration of an aliphatic group or a phenolic hydroxyl group of the resin. Further, metal oxidation can be suppressed by the rust-proof effect on the metal material.
Since the resin and the metal material can be simultaneously acted on, k is more preferably an integer of 2 to 4. R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination thereof, and the like, and may have a substituent. Among them, from the viewpoint of solubility in a developer or metal adhesion, the compound preferably has an alkyl ether group, -NH-, and more preferably-NH-from the viewpoint of interaction with a resin and metal adhesion by metal complex formation.
Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structures.
[ chemical formula 70]
Figure BDA0003775943360001021
[ chemical formula 71]
Figure BDA0003775943360001031
[ chemical formula 72]
Figure BDA0003775943360001041
[ chemical formula 73]
Figure BDA0003775943360001051
The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. When the amount is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation characteristics and the adhesion to the metal material after the reliability, and when the amount is more than 10 parts by mass, the sensitivity of the resin composition may be lowered by the interaction with the photosensitizer. The antioxidant may be used alone or in combination of two or more. When two or more kinds are used, the total amount of these is preferably within the above range.
< restrictions on other contained substances >
From the viewpoint of the properties of the coated surface, the moisture content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass. Examples of the method for maintaining the moisture content include adjustment of humidity under storage conditions, reduction of porosity of the storage container, and the like.
From the viewpoint of insulation properties, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities unexpectedly contained in the curable resin composition of the present invention, there can be mentioned the following methods: selecting a raw material having a small metal content as a raw material constituting the curable resin composition of the present invention; filtering a raw material constituting the curable resin composition of the present invention with a filter; the inside of the apparatus is lined with polytetrafluoroethylene or the like to conduct distillation or the like under conditions that minimize contamination.
In the curable resin composition of the present invention, in view of the use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm, from the viewpoint of corrosion of wiring. Among these, the substance present in the state of a halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above-mentioned range.
As a method of adjusting the content of the halogen atom, ion exchange treatment and the like can be preferably mentioned.
As the container for the curable resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the curable resin composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is made of 6 kinds of 6-layer resins or a bottle in which the 6 kinds of resins are used to form a 7-layer structure. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.
< use of curable resin composition >
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, the present invention can also be used for forming an insulating film, a stress buffer film, or the like of a semiconductor device.
The curable resin composition of the present invention is used for at least one storage of a storage container by cold storage at-15 to 16 ℃, and the filling ratio of the curable resin composition during cold storage is preferably 50 to 90% with respect to the total storage volume of the storage container.
It is presumed that the curable resin composition of the present invention can provide a resin film having excellent film thickness uniformity even after such storage.
The storage container may be the storage container.
The refrigeration temperature is preferably 1 to 12 ℃, more preferably 3 to 10 ℃.
The time for the cold storage (in the case of multiple cold storage, the total time of the multiple cold storage) is preferably 1 hour to 100 days, and more preferably 12 hours to 30 days.
The storage is preferably performed under a light-shielding condition.
The filling rate is calculated as the total volume of the curable resin composition relative to the total storage volume of the storage container, and is preferably 50 to 99%, more preferably 70 to 90%.
< preparation of curable resin composition >
The curable resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
In addition, filtration using a filter is preferably performed for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. As the filter, a filter previously cleaned with an organic solvent may be used. In the filter filtration process, a plurality of filters may be connected in series or in parallel for use. When a plurality of filters are used, filters having different pore sizes or different materials may be used in combination. Also, various materials may be filtered multiple times. In the case of filtration multiple times, it may be a loop filtration. Further, the filtration can be performed by pressurization. When the filtration is performed under pressure, the pressure to be applied is, for example, 0.01MPa to 1.0MPa, preferably 0.03MPa to 0.9MPa, more preferably 0.05MPa to 0.7MPa, and still more preferably 0.05MPa to 0.3 MPa.
In addition to filtration using a filter, a process of removing impurities using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
(resin film, cured film, laminate, semiconductor device, and methods for producing these)
Next, a resin film, a cured film, a laminate, a semiconductor device, and methods for producing these will be described.
The resin film of the present invention is obtained by applying the curable resin composition of the present invention to a substrate.
The method of application and the type of substrate are not particularly limited, but preferable examples include those in the film forming step described later.
The thickness of the resin film can be set to a thickness within a range described later, as the thickness of a cured film described later. For example, the film thickness of the resin film may be determined in consideration of shrinkage or the like caused by curing.
The cured film of the present invention is obtained by curing the curable resin composition of the present invention or the resin film of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more, and can also be set to 1 μm or more. The upper limit value may be 100 μm or less, or may be 30 μm or less.
The cured film of the present invention can be laminated with 2 or more layers, and further laminated with 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes 2 or more cured films and a metal layer between any of the cured films. For example, a preferable laminate includes a laminate having a layer structure in which at least 3 layers of a first cured film, a metal layer, and a second cured film are sequentially laminated. The first cured film and the second cured film are both the cured film of the present invention, and a preferable embodiment thereof includes, for example, an embodiment in which either one of the first cured film and the second cured film is a film obtained by curing the curable resin composition of the present invention. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film may be the same composition or may be different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.
Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, a sealing film, a substrate material (a base film or a cover film of a flexible printed wiring board, an interlayer insulating film), an insulating film for actual mounting as described above, and the like may be patterned by etching. For these applications, for example, SCIENCE AND techrolog co, ltd, "high functionalization and application TECHNOLOGY of polyimide" 4 months 2008, kaki ben yaming/prison, base and development of CMC Technical library "published in 11 months 2011, and" latest base and application of polyimide "compiled by japan polyimide/aromatic polymer research society," NTS inc., 8 months 2010, and the like can be referred to.
The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use thereof in etching molded components, the production of protective paints and dielectric layers in electronics, particularly microelectronics, and the like.
The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film-forming step of applying the curable resin composition of the present invention to a substrate to form a film (resin film).
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film to light, and a developing step of developing the film.
The method for producing a cured film of the present invention preferably further comprises the film forming step and, if necessary, the developing step, and further comprises a heating step of heating the film at 50 to 450 ℃.
Specifically, the method preferably includes the following steps (a) to (d).
(a) Film formation step for forming a film (curable resin composition layer) by applying the curable resin composition to a substrate
(b) An exposure step of exposing the film after the film formation step
(c) A developing step of developing the exposed film
(d) A heating step of heating the developed film at 50 to 450 DEG C
By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the thermal alkali generator is decomposed to obtain sufficient curability.
The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film according to the present invention. In the method for producing a laminate of the present embodiment, after the cured film is formed according to the method for producing a cured film, the step (a), the steps (a) to (c), and the steps (a) to (d) are further performed again. In particular, it is preferable to perform each step sequentially a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured films or between the cured films or on the portion provided with the cured films and between the cured films. In addition, when the laminate is produced, it is not necessary to repeat all the steps (a) to (d), and as described above, by performing the steps (a), preferably (a) to (c) or (a) to (d) at least a plurality of times, a laminate of cured films can be obtained.
< film formation step (layer formation step) >
The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) of applying the curable resin composition to a substrate to form a film (layer).
The resin film of the present invention can be obtained according to the film formation process.
The type of the substrate may be appropriately determined depending On the application, and is not particularly limited, and may be a substrate made of a semiconductor such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, or amorphous silicon, a substrate made of quartz, Glass, an optical film, a ceramic material, a vapor-deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, paper, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, or an electrode plate of a Plasma Display Panel (PDP). Further, a layer such as an adhesive layer or an oxide layer may be provided on the surface of these substrates. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate, a Cu substrate, and a molded (mold) resin substrate are more preferable.
Further, a layer such as an adhesive layer or an oxide layer formed of Hexamethyldisilazane (HMDS) or the like may be provided on the surface of these base materials.
As the substrate, for example, a plate-like substrate (substrate) can be used.
The shape of the substrate is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the substrate is, for example, 100 to 450mm, preferably 200 to 450mm, as long as it is circular. If the shape is rectangular, the length of the short side is, for example, 100 to 1000mm, preferably 200 to 700 mm.
When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
The curable resin composition is preferably applied to a substrate by coating.
Specifically, examples of the method to be applied include a dip coating method, an air knife coating method, a curtain coating method, a bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, an ink jet method, and the like. From the viewpoint of uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration or the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected depending on the shape of the substrate, and in the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an ink jet method, and the like are preferable, and in the case of a rectangular substrate, a slit coating method, a spray coating method, an ink jet method, and the like are preferable. In the case of spin coating, for example, the coating can be applied at a rotation speed of 300 to 3,500rpm for 10 to 180 seconds, and at a rotation speed of 500 to 2,000rpm for about 10 seconds to 1 minute.
Further, a method of transferring a coating film previously applied and formed on the temporary support by the above-described application method onto a substrate can also be applied. In addition, in order to obtain uniformity of film thickness, it is also possible to apply the coating by combining a plurality of rotation speeds.
As the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 of Japanese patent application laid-open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese patent application laid-open No. 2006-047592 can also be preferably used in the present invention.
Further, a step of removing an excess film may be performed at the end of the substrate. Examples of such a step include Edge Bead Rinsing (EBR), air knife (air knife), and back rinsing (back rinse).
Further, the following pre-wetting step may be adopted: before the resin composition is applied to a substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
< drying Process >
The production method of the present invention may include a step of drying the film (curable resin composition layer) after the film formation step (layer formation step) to remove the solvent. Preferably, the drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time may be, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of the solvent in the curable resin composition solution is large, vacuum drying and heat drying may be combined. The heating and drying are not particularly limited, and a hot plate, a hot air oven, or the like is used.
< Exposure Process >
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer) to light. The exposure amount is not particularly limited as long as the curable resin composition can be cured, and for example, the exposure amount is preferably 100 to 10,000mJ/cm in terms of exposure energy at a wavelength of 365nm 2 More preferably 200 to 8,000mJ/cm 2 。
The exposure wavelength can be suitably defined within the range of 190 to 1,000nm, preferably 240 to 550 nm.
When the exposure wavelength is described in relation to the light source, examples thereof include (1) semiconductor laser light (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser light, KrF excimer laser light (wavelength 248nm), ArF excimer laser light (wavelength 193nm), F2 excimer laser light (wavelength 157nm), and (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) 532nm for the second harmonic and 355nm for the third harmonic of YAG laser, and the like. For the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferable, and among them, exposure based on i-ray is preferable. Thereby, high exposure sensitivity can be obtained in particular. Also, from the viewpoint of handling and productivity, a broad (3 wavelengths of g, h, i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is preferable.
The mode of exposure is not particularly limited as long as it is a mode of exposing at least a part of a film including the resin composition of the present invention, but examples thereof include exposure using a photomask, exposure by a laser direct imaging method, and the like.
< developing Process >
The production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). For example, in the case of a negative-type curable resin composition, an unexposed portion (unexposed portion) is removed by development. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include a method of discharging a developing solution from a nozzle, a method of spraying a mist, and a method of immersing a base material in a developing solution, and the discharging from a nozzle can be preferably used. In the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer on the substrate in a substantially stationary state, a step of vibrating the developer with ultrasonic waves or the like, a step of combining these steps, and the like can be employed.
The development is performed using a developer. For example, in the case of a negative-type curable resin composition, a developer can be used without particular limitation as long as it can remove an unexposed portion (unexposed portion).
As the developer, a developer containing an organic solvent or an aqueous alkali solution can be used.
In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula into ChemBioDraw.
When the developer is a developer containing an organic solvent, examples of the ester include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, methyl ethyl 3-alkoxypropionate, etc.), Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and ethers such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, and the like, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like are preferable, and hydrocarbons such as toluene, xylene, anisole, limonene, and the like are preferable, sulfoxides such as dimethyl sulfoxide are preferable, and a mixture of these organic solvents is also preferable.
In the case where the developer is a developer containing an organic solvent, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention.
Further, a surfactant may be contained in the developer.
When the developer is a developer containing an organic solvent, the organic solvent is preferably contained in the developer in an amount of 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In the developer, 100% by mass may be an organic solvent.
When the developer is an aqueous alkaline solution, examples of the alkaline compound that can be contained in the aqueous alkaline solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, and the like, and TMAH is preferred. For example, when TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and still more preferably 0.3 to 3 mass% based on the total mass of the developer.
[ method of supplying developer ]
The method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the base material on which the film is formed in the developing solution, a method of spin immersion developing in which the developing solution is supplied to the film formed on the base material using a nozzle, and a method of continuously supplying the developing solution. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developer, the removability of the non-image portion, and the efficiency of the production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable, and a method of supplying the developer with a spray nozzle is more preferable from the viewpoint of the permeability of the developer to the image portion.
Further, the step of removing the developer from the base material by rotating the base material after continuously supplying the developer with the straight nozzle, removing the developer from the base material by rotating the base material, drying the developer by rotation, continuously supplying the developer with the straight nozzle again, and removing the developer from the base material by rotating the base material may be employed, and this step may be repeated a plurality of times.
As a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these steps, and the like can be employed.
The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, and the development can be usually carried out at 20 to 40 ℃.
After the treatment with the developer, rinsing may be further performed. The rinsing is preferably carried out in a solvent different from the developer. For example, propylene glycol monomethyl ether acetate may be mentioned. The rinsing time is preferably 5 seconds to 5 minutes. Further, a step of applying both the developing solution and the rinse solution may be included between the developing and the rinsing. The time for the above step is preferably 1 second to 5 minutes. For example, the solvent contained in the curable resin composition can be used for rinsing.
The rinse solution may also contain other components.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method of supplying rinse solution ]
The method of supplying the rinse solution is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinse solution, a method of supplying the substrate by spin immersion, a method of supplying the rinse solution to the substrate by a shower, and a method of continuously supplying the rinse solution to the substrate by a mechanism such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency of the production, there are methods of supplying the rinse liquid by a shower nozzle, a straight nozzle, a spray nozzle, or the like, preferably a method of continuously supplying by a spray nozzle, and more preferably a method of supplying by a spray nozzle from the viewpoint of the permeability of the rinse liquid to the image portion. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the exposed film with a straight nozzle or continuously supplying a rinsing liquid, and more preferably a step of supplying a rinsing liquid with a spray nozzle.
Further, as a method of supplying the developing solution in the rinsing step, a step of continuously supplying the rinsing solution to the substrate, a step of holding the rinsing solution on the substrate in a substantially stationary state, a step of vibrating the rinsing solution on the substrate by ultrasonic waves or the like, a step of combining these steps, and the like can be employed.
When the developing solution is a developing solution containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), and the like, and PGMEA is preferable. Water is preferable as a rinse liquid for development with a developer containing an aqueous alkali solution.
The rinsing time is preferably 5 seconds to 1 minute.
< heating Process >
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ℃.
The heating step is preferably included after the film formation step (layer formation step), the drying step, and the development step. In the heating step, for example, the thermal alkali generator decomposes to generate an alkali, thereby performing a cyclization reaction as a precursor of the specific resin. The curable resin composition of the present invention may contain a radical polymerizable compound other than a precursor of the specific resin, but curing of a radical polymerizable compound other than a precursor of the unreacted specific resin and the like may be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, further preferably 350 ℃ or lower, further preferably 250 ℃ or lower, and further preferably 220 ℃ or lower.
The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is set to 1 ℃/min or more, whereby the productivity can be ensured, and the excessive volatilization of the amine can be prevented, and the residual stress of the cured film can be reduced by setting the temperature increase rate to 12 ℃/min or less. In the case of an oven capable of rapid heating, the temperature is preferably raised at a rate of 1 to 8 ℃/sec, more preferably 2 to 7 ℃/sec, and still more preferably 3 to 6 ℃/sec, from the temperature at the start of heating to the maximum heating temperature.
The temperature at the start of heating is preferably from 20 ℃ to 150 ℃, more preferably from 20 ℃ to 130 ℃, and still more preferably from 25 ℃ to 120 ℃. The temperature at the start of heating is a temperature at which the step of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied to a substrate and then dried, it is preferable to gradually increase the temperature from the temperature of the film (layer) after drying, for example, from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the curable resin composition.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 180 to 320 ℃, and more preferably 180 to 260 ℃, from the viewpoint of adhesion between the layers of the cured film. The reason for this is not clear, but is considered to be because the ethynyl groups of the specific resin between the layers undergo a crosslinking reaction with each other by setting the temperature to this temperature.
The heating may be performed in stages. As an example, the following pretreatment process may be performed: the temperature was raised at 3 ℃ per minute from 25 ℃ to 180 ℃ and held at 180 ℃ for 60 minutes, and at 2 ℃ per minute from 180 ℃ to 200 ℃ and held at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. By such a pretreatment step, the properties of the film can be further improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in 2 stages or more, and for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.
Further, the heating and cooling may be performed, and the cooling rate at this time is preferably 1 to 5 ℃/min.
In order to prevent the decomposition of the specific resin, it is preferable to perform the heating step in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon and performing the heating step in a vacuum. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.
The heating mechanism is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric oven, and a hot air oven.
< Process for Forming Metal layer >
The production method of the present invention preferably includes a metal layer formation step of forming a metal layer on the surface of the developed film (curable resin composition layer).
The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper, aluminum, and alloys containing these metals, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be applied. For example, photolithography, lift off (lift off), electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, there are a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.
< laminating Process >
The production method of the present invention preferably further comprises a lamination step.
The laminating step is a series of steps including (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step, which are sequentially performed again on the surface of the cured film (resin layer) or the metal layer. However, the film forming step (a) may be repeated. Further, the following method may be adopted: the heating step (d) is performed at the end of or in the middle of the lamination. That is, the following method can be adopted: the steps (a) to (c) are repeated a predetermined number of times, and then (d) is heated to collectively cure the stacked curable resin composition layers. In addition, the developing step (c) may be followed by the metal layer forming step (e), and in this case, the heating step (d) may be performed every time or may be performed after stacking a predetermined number of times. It goes without saying that the laminating step may appropriately include the drying step, the heating step, and the like.
In the case where the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer formation step. As the surface activation treatment, plasma treatment may be exemplified.
The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and still more preferably 3 to 5 times.
Each layer in the laminating step may be the same layer in composition, shape, film thickness, or the like, or may be different layers.
For example, the resin layer is preferably 2 to 20 layers, more preferably 3 to 7 layers, and still more preferably 3 to 5 layers, as in the case of resin layer/metal layer/resin layer/metal layer.
In the present invention, it is particularly preferable that after the metal layer is provided, a cured film (resin layer) of the curable resin composition is further formed so as to cover the metal layer. Specifically, there may be mentioned a method in which the film formation step (a), the exposure step (b), the development step (c), the metal layer formation step (e), and the heating step (d) are repeated in this order, or a method in which the film formation step (a), the exposure step (b), the development step (c), and the metal layer formation step (e) are repeated in this order, and the heating step (d) is provided at the end or at the middle of the process. The curable resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step.
(surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of performing a surface activation treatment on at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the resin composition layer after the above-described development step.
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, or may be performed on at least a part of each of the metal layer and the resin composition layer after exposure. Preferably, at least a part of the metal layer is subjected to a surface activation treatment, and preferably, a part or all of a region of the metal layer on the surface of which the resin composition layer is formed is subjected to a surface activation treatment. By thus subjecting the surface of the metal layer to surface activation treatment, adhesion to the resin composition layer (film) provided on the surface can be improved.
Further, it is preferable that a part or the whole of the resin composition layer (resin layer) after exposure is also subjected to surface activation treatment. In this manner, by subjecting the surface of the resin composition layer to surface activation treatment, the adhesion to the metal layer or the resin layer provided on the surface subjected to surface activation treatment can be improved. In particular, when the resin composition layer is cured, for example, during negative-type development, the resin composition layer is less likely to be damaged by surface treatment, and adhesion is likely to be improved.
The surface activation treatment is specifically selected from the group consisting of plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF-based treatment 4 /O 2 、NF 3 /O 2 、SF 6 、NF 3 、NF 3 /O 2 The etching treatment of (1), the surface treatment by an Ultraviolet (UV) ozone method, the treatment of immersing in an aqueous hydrochloric acid solution to remove an oxide film, then immersing in an organic surface treatment agent containing a compound of at least one of an amino group and a thiol group, and the mechanical roughening treatment using a brush are preferably plasma treatment, and particularly preferably oxygen plasma treatment using oxygen in a raw material gas. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m 2 More preferably 1000 to 100,000J/m 2 Most preferably 10,000 to 50,000J/m 2 。
Semiconductor devices comprising the cured films or laminates of the invention are also disclosed. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of japanese patent application laid-open No. 2016-027357 and the descriptions in fig. 1, which are incorporated herein.
Examples
The present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are on a mass basis.
< examples and comparative examples >
In each example, the components described in tables 1 to 7 below were mixed to obtain each curable resin composition. In each comparative example, the components shown in table 2 below were mixed to obtain each composition for comparison.
Specifically, the contents of components other than the solvents described in tables 1 to 7 were set to the amounts (parts by mass) described in the columns of tables 1 to 7. In each composition, the total content of the solvents is such that the solid content concentration (mass%) of the composition is a value described in tables 1 to 7, and the content ratio of each solvent is a mass ratio based on the numerical values described in the columns of tables 1 to 7.
The obtained curable resin composition and comparative composition were subjected to pressure filtration through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In tables 1 to 7, "-" indicates that the composition does not contain the corresponding component.
[ Table 1]
Figure BDA0003775943360001201
[ Table 2]
Figure BDA0003775943360001211
[ Table 3]
Figure BDA0003775943360001221
[ Table 4]
Figure BDA0003775943360001231
[ Table 5]
Figure BDA0003775943360001241
[ Table 6]
Figure BDA0003775943360001251
[ Table 7]
Figure BDA0003775943360001261
The details of each component described in tables 1 to 7 are as follows.
[ resin (specific resin) ])
A-1: a resin having a structure represented by the following formula (A-1)
A-101: resin synthesized by Synthesis example 1
A-201: resin synthesized by synthetic example 2 described below
[ chemical formula 74]
Figure BDA0003775943360001271
[ Synthesis example 1: synthesis of polyimide precursor A-101 ]
In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 9.49g (32.25 mmol) of 4, 4' -biphenyltetracarboxylic dianhydride and 10.0g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140mL of diglyme while removing water. 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 0.05g of pure water and 10.7g (135 mmol) of pyridine were successively added thereto, and the mixture was stirred at 60 ℃ for 18 hours. Subsequently, after the mixture was cooled to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride can be obtained. Subsequently, after the mixture was warmed to room temperature (23 ℃) and stirred for 2 hours, 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Subsequently, to the obtained transparent solution was added dropwise over 1 hour a solution obtained by dissolving 11.8g (58.7 mmol) of 4, 4' -diaminodiphenyl ether in NMP100 mL. Subsequently, methanol 5.6g (17.5 mmol) and 3, 5-di-tert-butyl-4-hydroxytoluene 0.05g were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and stirred again in 4 liters of water for 30 minutes and filtered again. Subsequently, the obtained polyimide precursor resin was dried at 45 ℃ for 3 days under a reduced pressure, thereby obtaining a polyimide precursor a-101.
[ Synthesis example 2: synthesis of polybenzoxazole precursor A-201
73.25g (0.200mol) of hexafluoro-2, 2-Bis (3-amino-4-hydroxyphenyl) propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 31.64g (0.400mol) of pyridine and 293g of NMP were added to a three-necked flask equipped with a thermometer, a stirrer and a nitrogen introduction tube. It was stirred at room temperature (23 ℃) and then cooled to-15 ℃ with a dry ice/methanol bath. A mixed solution of 30.11g (0.144mol) of a 30 mass% NMP solution of 1, 4-cyclohexanedicarboxylic acid dichloride and 3.83g (0.016mol) of sebasic Chloride (Sebacyl Chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25g of NMP was added dropwise to the solution while maintaining the reaction temperature at-5 ℃ to-15 ℃. After the end of the dropwise addition, the obtained mixture was stirred at room temperature for 16 hours.
Then, the reaction solution was cooled to-5 ℃ or lower with an ice/methanol bath, and a mixture of 9.59g (0.090mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.5g of NMP was added dropwise while maintaining the reaction temperature at-0 ℃ or lower. After the end of the dropwise addition, stirring was further carried out for 16 hours.
The reaction solution was diluted with NMP550g and poured into a vigorously stirred 4L deionized water/methanol (80/20 vol/vol) mixture, and the precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was dried at 50 ℃ for two days under vacuum, thus obtaining resin A-1 a.
To a 500mL eggplant-shaped flask were added 25.00g of resin A-1a, 125g of NMP, and 125g of methyl ethyl ketone, and the mixture was concentrated under reduced pressure at 60 ℃ until the content became 160 g. To the contents were added 0.43g (1.85mmol) of camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.12g (0.065mol) of 2, 3-dihydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) and stirred at room temperature (23 ℃ C.) for 1.5 hours. To the obtained solution, 0.37g of triethylamine and NMP150g were added for dilution.
The obtained solution was put into a vigorously stirred 2L mixture of deionized water/methanol (80/20 vol), and the precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was dried at 50 ℃ for two days under vacuum, thereby obtaining Polybenzoxazole (PBO) precursor a-201.
(crosslinking agent)
B-1: a compound of the structure
B-2: dipentaerythritol hexaacrylate
B-3: LIGHT ESTER BP-6EM (Kyoeisha chemical Co., Ltd.; manufactured by Ltd.)
[ chemical formula 75]
Figure BDA0003775943360001281
[ polymerization initiator (photopolymerization initiator) ]
C-1: a compound of the structure
C-2: irgacure OXE-01 (manufactured by BASF corporation)
C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION)
[ chemical formula 76]
Figure BDA0003775943360001291
[ sealing agent (silane coupling agent) ]
D-1: a compound of the structure
D-2: n- [3- (triethoxysilyl) propyl ] maleamic acid D-3: 3-methacryloxypropyltrimethoxysilane
[ chemical formula 77]
Figure BDA0003775943360001292
[ polymerization inhibitor ]
E-1: a compound of the structure
E-2: 4-methoxyphenol
E-3: 2-nitroso-1-naphthol
[ chemical formula 78]
Figure BDA0003775943360001293
[ migration inhibitor ]
F-1: a compound of the structure
F-2: 5-amino-1H-tetrazoles
F-3: 3-amino-1, 2, 4-triazoles
F-4: 3, 5-diamino-1, 2, 4-triazoles
F-5: adenine
[ chemical formula 79]
Figure BDA0003775943360001301
[ thermoalcogenating agent ]
G-1: a compound of the structure
G-2: a compound of the structure
G-3: a compound of the structure
[ chemical formula 80]
Figure BDA0003775943360001302
[ solvent ]
NMP: n-methyl-2-pyrrolidone
DMSO: dimethyl sulfoxide
EL: lactic acid ethyl ester
GBL: gamma-butyrolactone
Cyptn: cyclopentanone
EA: 3-butoxy-N, N-dimethylpropionamide
PGMEA: propylene glycol monomethyl ether acetate
< evaluation >
[ evaluation of film thickness uniformity based on composition immediately after preparation ]
In each of examples and comparative examples, each of the curable resin compositions and comparative compositions immediately after preparation was applied (coated) in a layer form onto a circular silicon wafer having a diameter of 8 inches by a spin coating method.
The coated silicon wafer was dried on a hot plate at 100 ℃ for 4 minutes to form a resin film having a film thickness of 19 μm on the silicon wafer. The film thickness is set as the arithmetic average of the film thicknesses at 10 points in the plane.
The film thickness of the resin film on the diameter of the silicon wafer is measured at 10 points in total at equal intervals including both ends of the resin film, and the difference between the maximum value and the minimum value of the measured values at the 10 points is defined as the in-plane maximum film thickness difference (μm).
The film thickness uniformity of the composition immediately after the preparation was evaluated according to the following evaluation criteria. The evaluation results are shown in the column "film thickness uniformity (immediately after production)" in tables 1 to 7. It can be said that the smaller the in-plane maximum film thickness difference (μm), the more excellent the film thickness uniformity of the resin film.
Evaluation criteria-
10: the maximum difference in thickness (μm) in the plane is 0.5 μm or less.
9: the maximum difference in-plane thickness (μm) is more than 0.5 μm and 0.6 μm or less.
8: the maximum difference in-plane thickness (μm) is more than 0.6 μm and 0.7 μm or less.
7: the maximum difference in-plane thickness (μm) is more than 0.7 μm and 0.8 μm or less.
6: the maximum difference in-plane thickness (μm) is more than 0.8 μm and 0.9 μm or less.
5: the maximum difference in-plane thickness (μm) is more than 0.9 μm and 1.0 μm or less.
4: the maximum difference in-plane thickness (μm) is more than 1.0 μm and 1.1 μm or less.
3: the maximum difference in-plane thickness (μm) is more than 1.1 μm and 1.2 μm or less.
2: the maximum difference in-plane thickness (. mu.m) is more than 1.2 μm and not more than 1.3. mu.m.
1: the maximum difference in-plane thickness (. mu.m) is more than 1.3. mu.m.
[ evaluation based on film thickness uniformity of composition after 6 months of preparation ]
In each of examples and comparative examples, each of the curable resin compositions and comparative compositions immediately after preparation was put in a storage container and sealed, and storage under light-shielding conditions at 7 ℃ and 23 ℃ was repeated every 24 hours for 6 months. The filling rate of the curable resin composition was 90% of the total storage volume of the storage container.
After the above storage, in each of examples and comparative examples, each of the curable resin compositions and comparative compositions was returned to room temperature (23 ℃), applied (coated) in a layer form onto a circular silicon wafer having a diameter of 8 inches by a spin coating method, and dried on a hot plate at 100 ℃ for 4 minutes to form a resin film. The coating conditions and the amount of the composition used in the spin coating method were set to be the same as those in the spin coating method in terms of the film thickness uniformity immediately after the production.
Thereafter, the in-plane maximum difference in film thickness (μm) was calculated in the same manner as the above evaluation based on the film thickness uniformity of the composition immediately after the production, and the film thickness uniformity of the composition 6 months after the production was evaluated by the same evaluation criterion as that in the evaluation based on the film thickness uniformity of the composition immediately after the production. The evaluation results are shown in the column "film thickness uniformity (after 6 months of preparation)" in tables 1 to 7. It can be said that the smaller the in-plane maximum film thickness difference (μm), the more excellent the film thickness uniformity of the resin film.
[ evaluation of resolution based on composition immediately after preparation ]
In each of examples and comparative examples, a resin film was formed on a silicon wafer having a circular shape and a diameter of 8 inches by the same method as the above evaluation of the film thickness uniformity based on the composition immediately after the preparation.
After that, the resin film was exposed through a mask containing a fuse box (fuse box) of 5 μm to 25 μm in 1 μm scale.
The exposure is performed by an i-ray using a stepper (Nikon NSR2005 i9C), and the exposure amount at a wavelength of 365nm is 200-400 mJ/cm 2 When the exposure amount is changed, the exposure amount with the minimum line width described later is used.
After the above exposure, the resin film was developed using cyclopentanone at 30 ℃ as a developer, and washed with PGMEA (propylene glycol monomethyl ether acetate).
The pattern after the above-mentioned washing was observed by an optical microscope, and an arithmetic average of a minimum line width of the silicon wafer exposed at the bottom of the fuse box among line widths of 5 μm to 25 μm in 1 μm scale was set as a "minimum line width", and evaluated according to the following evaluation criteria. The evaluation results are shown in the column "resolution (immediately after preparation)" of tables 1 to 7. It can be said that the smaller the minimum line width, the more excellent the resolution (photolithography).
Evaluation criteria-
10: the minimum line width is 7 μm or less.
9: the minimum line width is more than 7 μm and 8 μm or less.
8: the minimum line width is more than 8 μm and 9 μm or less.
7: the minimum line width is more than 9 μm and 11 μm or less.
6: the minimum line width is more than 11 μm and 13 μm or less.
5: the minimum line width is more than 13 μm and 16 μm or less.
4: the minimum line width is more than 16 μm and not more than 19 μm.
3: the minimum line width is more than 19 μm and 22 μm or less.
2: the minimum line width is more than 22 μm and not more than 24 μm.
1: the minimum line width is more than 24 μm.
[ evaluation based on resolution of composition after 6 months of preparation ]
In each of the examples and comparative examples, the curable resin compositions and comparative compositions immediately after the preparation were stored for 6 months by the same method as described in the above "evaluation of film thickness uniformity of compositions after 6 months of preparation".
After the storage, in each of the examples and comparative examples, the curable resin compositions and comparative compositions were returned to room temperature (23 ℃) and then evaluated by the same evaluation methods and evaluation criteria as those described above in "evaluation of resolution based on compositions immediately after production". The evaluation results are shown in the column "resolution (after 6 months of preparation)" in tables 1 to 7.
[ evaluation of chemical resistance based on composition immediately after preparation ]
In each of examples and comparative examples, a resin film was formed on a silicon wafer having a circular shape with a diameter of 8 inches by the same method as the above evaluation of the film thickness uniformity based on the composition immediately after the preparation.
Using a stepper (Nikon NSR 2005i9C), at 200mJ/cm 2 The entire surface of the resin film on the silicon wafer is exposed to the exposure energy of (2).
The entire surface of the resin film after exposure was heated at a temperature rising rate of 10 ℃/min under a nitrogen atmosphere and at 200 ℃ for 120 minutes to obtain a cured film.
The cured film obtained was immersed in the following chemical solution under the following evaluation conditions, and evaluated.
Liquid medicine: the set temperature was 75 deg.C
The following composition of the drug solution was used.
Dimethyl sulfoxide (DMSO) 70% by mass
Tetramethylammonium hydroxide (TMAH) 2.5% by mass
10% by mass of 3-methoxy-3-methyl-1-butanol
Rest of water
Evaluation conditions were as follows: the cured film was immersed in the chemical solution for 15 minutes, washed with water, and then the film thicknesses before and after immersion were compared to calculate the residual film ratio (%) by the following formula.
Residual film ratio (%) (% of film thickness of cured film after immersion)/film thickness of cured film before immersion (μm) × 100
The evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the column "chemical resistance (immediately after preparation)" of tables 1 to 7. It can be said that the greater the residual film ratio (%), the more excellent the chemical resistance.
Evaluation criteria-
10: the residual film ratio (%) is 90.0% or more.
9: the residual film ratio (%) is 89.0% or more and less than 90.0%.
8: the residual film ratio (%) is 88.0% or more and less than 89.0%.
7: the residual film ratio (%) is 87.0% or more and less than 88.0%.
6: the residual film ratio (%) is 86.0% or more and less than 87.0%.
5: the residual film ratio (%) is 85.0% or more and less than 86.0%.
4: the residual film ratio (%) is 84.0% or more and less than 85.0%.
3: the residual film ratio (%) is 83.0% or more and less than 84.0%.
2: the residual film ratio (%) is 82.0% or more and less than 83.0%.
1: the residual film rate (%) was less than 82.0%.
[ evaluation of chemical resistance based on preparation of composition after 6 months ]
In each of the examples and comparative examples, the curable resin compositions and comparative compositions immediately after the preparation were stored for 6 months by the same method as described in the above "evaluation of film thickness uniformity of compositions after 6 months of preparation".
After the storage, in each of the examples and comparative examples, the curable resin compositions and comparative compositions were returned to room temperature (23 ℃) and then evaluated by the same methods and evaluation criteria as in the "evaluation of chemical resistance based on the composition immediately after the preparation". The evaluation results are shown in tables 1 to 7 under the column "chemical resistance (after 6 months of preparation)".
[ comprehensive evaluation ]
In each example or comparative example, evaluation points were calculated by the following formulas, and comprehensive evaluation was performed according to the following evaluation criteria. The evaluation points are shown in the column of "comprehensive evaluation (after 6 months of preparation)" in tables 1 to 7. The larger the evaluation point, the more suitable the solvent is for practical use. The weighting is derived by considering the knowledge of the items that have affected the physical properties of the film when the permanent film is finally produced in the same system in the past.
Evaluation point ═ (evaluation result based on film thickness uniformity of composition after 6 months of production × 3+ evaluation result based on resolution of composition after 6 months of production × 2+ evaluation result based on chemical resistance of composition after 6 months of production)/6
From the above results, it is understood that the curable resin composition of the present invention is excellent in the uniformity of film thickness of the obtained resin film even after 6 months of storage.
The comparative composition of comparative example 1 contained only one solvent. It is found that the comparative composition of comparative example 1 has poor film thickness uniformity of the obtained resin film after 6 months of storage.
< example 101 >
The curable resin composition used in example 1 was applied in a layer form to the surface of a thin copper layer of a resin substrate having a thin copper layer formed on the surface thereof by spin coating, dried at 100 ℃ for 4 minutes to form a curable resin composition layer having a thickness of 20 μm, and then exposed to light using a stepper (Nikon co., ltd., NSR1505 i 6). The exposure was carried out at a wavelength of 365nm through a mask (binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm). After exposure, the plate was heated at 100 ℃ for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsing was performed with PGMEA for 30 seconds, thereby obtaining a pattern of a layer.
Subsequently, the temperature was raised to 200 ℃ at a temperature raising rate of 10 ℃/min in a nitrogen atmosphere, and then the temperature was maintained at 200 ℃ for 120 minutes, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer has excellent insulating properties.
Then, a semiconductor device was manufactured using the interlayer insulating film for the rewiring layer, and as a result, it was confirmed that the semiconductor device was operating normally.

Claims (17)

1. A curable resin composition comprising:
at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor; and
at least two solvents.
2. The curable resin composition according to claim 1, further comprising a migration inhibitor,
the migration inhibitor is a compound having at least one heterocycle selected from the group consisting of an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring and a triazine ring, and an amino group.
3. The curable resin composition according to claim 1 or 2, further comprising a migration inhibitor,
the migration inhibitor is at least one compound selected from the group consisting of 5-methylbenzotriazole, 3-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole and 5-amino-1H-tetrazole.
4. The curable resin composition according to any one of claims 1 to 3,
the solvent contains dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate relative to the total mass of the solvent is more than 40 mass%, and the content of gamma-butyrolactone relative to the total mass of the solvent is less than 40 mass%.
5. The curable resin composition according to any one of claims 1 to 4,
the solvent includes a solvent having a nitrogen-containing heterocyclic structure.
6. The curable resin composition according to any one of claims 1 to 5,
the solvent includes a solvent having an ether bond.
7. The curable resin composition according to any one of claims 1 to 6,
the solvent having the content of the 2 nd-order solvent is contained in an amount of 20 mass% or more based on the total mass of the solvents.
8. The curable resin composition according to any one of claims 1 to 7, further comprising a silane coupling agent.
9. The curable resin composition according to any one of claims 1 to 8, which is used for storage in a storage container at least once under refrigeration at-15 ℃ to 16 ℃, and the filling rate of the curable resin composition during refrigeration is 50% to 90% relative to the total storage volume of the storage container.
10. The curable resin composition according to any one of claims 1 to 9, which is used for formation of an interlayer insulating film for a rewiring layer.
11. A resin film obtained by applying the curable resin composition according to any one of claims 1 to 10 to a substrate.
12. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 10 or the resin film according to claim 11.
13. A laminate comprising 2 or more layers of the cured films of claim 12 and a metal layer between any of the cured films.
14. A method of manufacturing a cured film, comprising:
a film forming step of applying the curable resin composition according to any one of claims 1 to 10 to a substrate to form a film.
15. The method for manufacturing a cured film according to claim 14, comprising:
an exposure step of exposing the film and a development step of developing the film.
16. The method for manufacturing a cured film according to claim 14 or 15, comprising:
a heating step of heating the film at 50 to 450 ℃.
17. A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.
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