CN112639618A - Negative photosensitive resin composition - Google Patents

Negative photosensitive resin composition Download PDF

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Publication number
CN112639618A
CN112639618A CN201980056292.1A CN201980056292A CN112639618A CN 112639618 A CN112639618 A CN 112639618A CN 201980056292 A CN201980056292 A CN 201980056292A CN 112639618 A CN112639618 A CN 112639618A
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group
component
photosensitive resin
negative photosensitive
resin composition
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Inventor
铃木朋哉
安达勋
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Nissan Chemical Corp
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Nissan Chemical Corp
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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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

Abstract

The present invention addresses the problem of providing a novel negative photosensitive resin composition. The negative photosensitive resin composition comprises a component (A), a component (B) which is 80 to 90 mass% relative to 100 mass% of the component (A), a component (C) which is 3 to 20 mass% relative to 100 mass% of the total amount of the component (B), and a solvent. (A) The components: an alkali-soluble polymer, (B) component: 1 at least 2 crosslinkable compounds having 2 or more polymerizable groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group and a vinyl group in a molecule, and a component (C): at least 1 photopolymerization initiator.

Description

Negative photosensitive resin composition
Technical Field
The present invention relates to a negative photosensitive resin composition containing an alkali-soluble polymer, at least 2 crosslinkable compounds, at least 1 photopolymerization initiator, and a solvent. In particular, the present invention relates to a negative photosensitive resin composition for forming a microlens.
Background
Conventionally, in an electronic device such as a CCD/CMOS image sensor, a microlens is provided in order to improve light collection efficiency. As one of methods for manufacturing a microlens for a CCD/CMOS image sensor, an etch-back method is known (patent document 1 and patent document 2). That is, a resist pattern is formed on a microlens resin layer formed on a color filter, and the resist pattern is reflowed by heat treatment to form a lens pattern. The resin layer for microlenses in the lower layer is etched back using the lens pattern formed by reflowing the resist pattern as an etching mask, and the lens pattern shape is transferred to the resin layer for microlenses, thereby producing microlenses. Such microlenses are required to have various properties such as chemical resistance and high transparency.
Further, in the case where a film is patterned only at an arbitrary position on an electronic device element such as a CCD/CMOS image sensor, a liquid crystal display, and an organic EL display, photolithography is required. Such a photosensitive material is required to be capable of forming a pattern (sensitivity characteristic) with a low exposure amount and suppressing generation of residue after alkali development.
Further, a photosensitive resin composition for forming a microlens containing a maleimide copolymer (patent document 3) and a positive resist composition containing a triazine skeleton (patent document 4) have been proposed. However, these patent documents require high-temperature heating at temperatures exceeding 100 ℃, for example, 140 ℃ to 260 ℃ in order to satisfy the above-mentioned various properties, particularly solvent resistance, and cannot satisfy the above-mentioned properties by low-temperature heating at temperatures of 100 ℃ or less.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 1-10666
Patent document 2: japanese laid-open patent publication No. 6-112459
Patent document 3: japanese patent No. 5867735
Patent document 4: japanese patent No. 5673963
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a negative photosensitive resin composition which can remarkably improve high transparency, solvent resistance, sensitivity characteristics, and residue at an unexposed portion of a film obtained at a baking temperature of 100 ℃.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, the present invention has been completed. That is, the present invention is a negative photosensitive resin composition containing the following component (a), the following component (B) in an amount of 80 to 90 mass% relative to 100 mass% of the component (a), the following component (C) in an amount of 3 to 20 mass% relative to 100 mass% of the total amount of the component (B), and a solvent.
(A) The components: alkali soluble polymer
(B) The components: 1 at least 2 kinds of crosslinkable compounds having 2 or more polymerizable groups selected from the group consisting of acryloyloxy group, methacryloyloxy group, allyl group and vinyl group in the molecule
(C) The components: at least 1 photopolymerization initiator
The at least 2 kinds of crosslinkable compounds include, for example, a crosslinkable compound having 2 acryloyloxy groups or methacryloyloxy groups as the polymerizable group in 1 molecule, and a crosslinkable compound having 3 or more acryloyloxy groups or methacryloyloxy groups as the polymerizable group in 1 molecule.
The alkali-soluble polymer has, for example, a structural unit selected from the following formulae (1a), (1b), (1c), (1d) and (1 e).
Figure BDA0002953450740000031
(in the formula, R1Represents a hydrogen atom or a methyl group, A represents an-O-group or an-NH-group, X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or a divalent linking group containing an alkyleneoxy group having 1 to 3 carbon atoms, and Z1Represents hydroxyphenyl or carboxyphenyl, Z2Represents hydroxyphenyl, carboxyphenyl or carboxyl, Z3Represents a hydrogen atom, a hydroxyphenyl group or a carboxyphenyl group. )
The divalent linking group is, for example, the C1-3 alkylene oxide group, or 2 or more of the C1-3 alkylene oxide groups bonded together.
The alkali-soluble polymer is, for example, a copolymer further having a structural unit different from the structural unit described above and selected from the following formulae (2a), (2b) and (2 c).
Figure BDA0002953450740000032
(in the formula, R1Represents a hydrogen atom or a methyl group, A represents an-O-group or an-NH-group, X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or a divalent linking group containing an alkyleneoxy group having 1 to 3 carbon atoms, and Z4Represents a linear organic group having 1 to 3 carbon atoms or a branched or cyclic organic group having 3 to 14 carbon atoms. )
The divalent linking group is, for example, the C1-3 alkylene oxide group, or 2 or more of the C1-3 alkylene oxide groups bonded together. The organic group may have at least 1 heteroatom such as a nitrogen atom or an oxygen atom, and may have a double bond or a triple bond between 2 carbon atoms or between a carbon atom and a heteroatom. Examples of the cyclic organic group include an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a bridged hydrocarbon group, and a heterocyclic group.
The negative photosensitive resin composition of the present invention is used for forming a microlens, for example.
The present invention is also a method for manufacturing a microlens, including the steps of: a step of coating the negative photosensitive resin composition on a substrate and pre-baking the composition to form a resin film; exposing the resin film through a mask; developing the exposed resin film with an alkaline developer; and exposing the entire surface of the developed resin film.
The method may further comprise a step of post-baking the resin film after or before the step of exposing the entire surface of the developed resin film.
ADVANTAGEOUS EFFECTS OF INVENTION
By optimizing the amounts of the alkali-soluble polymer, the at least 2 kinds of crosslinkable compounds, and the at least 1 kind of photopolymerization initiator to be added, a film obtained at a baking temperature of 100 ℃ using the composition can be highly transparent, and has high sensitivity, less residue in unexposed portions, and excellent solvent resistance. Therefore, the negative photosensitive resin composition of the present invention is suitable as a material for forming a microlens.
Detailed Description
The present invention is a negative photosensitive resin composition containing a component (A), a component (B) in an amount of 80 to 90% by mass relative to 100% by mass of the component (A), a component (C) in an amount of 3 to 20% by mass relative to 100% by mass of the total amount of the component (B), and a solvent. The details of the components of the present invention are described below. The solid content after removing the solvent from the negative photosensitive resin composition of the present invention is usually 1 to 50% by mass. In the present specification, the components of the negative photosensitive resin composition of the present invention other than the solvent are defined as solid components.
< component (A) >
The component (a) in the negative photosensitive resin composition of the present invention is an alkali-soluble polymer. The polymer is a polymer of a raw material monomer containing a monomer having an alkali-soluble group and any other monomer. (A) The alkali-soluble polymer of the component (a) may have an alkali-soluble group, and the type of the skeleton and side chain of the main chain of the polymer constituting the polymer is not particularly limited. The weight average molecular weight of the alkali-soluble polymer is, for example, 1000 to 50000, preferably 3000 to 40000. In addition, the weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample.
Examples of the alkali-soluble group-containing monomer include a carboxyl group-containing monomer, a phenolic hydroxyl group-containing monomer, an acid anhydride group-containing monomer, and a maleimide group-containing monomer.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and 4-vinylbenzoic acid.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide.
Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
Examples of the monomer having a maleimide group include the above-mentioned N- (carboxyphenyl) maleimide, N- (hydroxyphenyl) maleimide and maleimide.
Among the above monomers having an alkali-soluble group, preferred is a polymer containing at least 1 monomer selected from acrylic acid, methacrylic acid, maleic anhydride, and maleimide.
Further, the alkali-soluble polymer of the (a) component may be a copolymer of the above-mentioned monomer having an alkali-soluble group with other monomer. The copolymer is not limited to a copolymer obtained from 2 monomers, and may be a terpolymer (terpolymer) obtained from 3 monomers. Specific examples of the other monomer include, for example, an acrylate compound, a methacrylate compound, an N-substituted maleimide compound, an acrylonitrile compound, an acrylamide compound, a methacrylamide compound, a styrene compound and a vinyl compound. Specific examples of the other monomers are given below, but the monomers are not limited thereto.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, phenyl acrylate, phenoxyethyl acrylate, 2,2, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and mixtures thereof, 4-hydroxybutyl acrylate, 2, 3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, acryloyloxyethyl isocyanate, 8-ethyl-8-tricyclodecanyl acrylate, glycidyl acrylate.
Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, and the like, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, methacryloyloxyethyl isocyanate, 8-ethyl-8-tricyclodecyl methacrylate, glycidyl methacrylate.
Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.
Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.
The acrylonitrile compound may be, for example, acrylonitrile.
The addition ratio of the monomer having an alkali-soluble group to the other monomer is preferably 5 to 50 mass%/50 to 95 mass%. When the addition ratio of the monomer having an alkali-soluble group to the other monomer is too small, the unexposed portion is not dissolved in the developer, and thus tends to cause a residual film or residue. In addition, when the addition ratio of the monomer having an alkali-soluble group to the other monomer is too large, there is a possibility that the exposed portion is insufficient in curability and a pattern cannot be formed.
The method for obtaining the alkali-soluble polymer of the component (a) is not particularly limited, but it is generally obtained by subjecting a raw material monomer containing the above-mentioned monomer having an alkali-soluble group to a polymerization reaction in a polymerization solvent, usually at a temperature of 50 to 110 ℃.
The alkali-soluble polymer obtained by the above method has a structural unit selected from the group consisting of the above formula (1a), formula (1b), formula (1c), formula (1d) and formula (1 e). The alkali-soluble polymer may further have a structural unit different from the above structural unit selected from the group consisting of the above formula (2a), formula (2b) and formula (2 c).
The content of the component (a) in the negative photosensitive resin composition of the present invention is usually 48 to 55% by mass based on the content of the solid component in the composition.
< ingredient (B) >
The component (B) in the negative photosensitive resin composition of the present invention is at least 2 kinds of crosslinkable compounds having 2 or more polymerizable groups selected from an acryloyloxy group, a methacryloyloxy group, an allyl group and a vinyl group in 1 molecule. The component (B) is preferably a combination of a crosslinkable compound having 2 polymerizable groups in 1 molecule and a crosslinkable compound having 3 or more polymerizable groups in 1 molecule. The polymerizable group is present at the molecular end of the crosslinkable compound.
The crosslinkable compound of the component (B) is preferably a compound having a weight average molecular weight of 200 to 1,000, from the viewpoint of having good compatibility with other components of the negative photosensitive resin composition of the present invention and not affecting developability.
Examples of the crosslinkable compound include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethylacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3, 5-triacryloylhexahydro-triazine, 1,3, 5-trimethylacryloylhexahydro-sym-triazine, tris (hydroxyethylacryloyl) isocyanurate, and mixtures thereof, Tris (hydroxyethyl methacryloyl) isocyanurate, triacrylformal, trimethacryloyl formal, 1, 6-hexanediol acrylate, 1, 6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N '-bis (acryloyl) cysteine, N' -bis (methacryloyl) cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, and mixtures thereof, Bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanolfluorene diacrylate, bisphenoxyethanolfluorene dimethacrylate, diallyl ether bisphenol A, o, o' -diallyl bisphenol A, diallyl maleate, triallyl trimellitate.
The crosslinkable compound can be easily obtained as a commercially available product, and examples thereof include, KAYARAD (registered trademark) T-1420, KAYARAD DPHA, KAYARAD DPHA-2C, KAYARAD-310, KAYARAD-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DN-0075, KAYARAD DN-2475, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYA R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD PET-30, KAYARAD RP-1040 (above, made by Nippon chemical Co., Ltd.); アロニックス (registered trademark) M-210, アロニックス M-208, アロニックス M-211B, アロニックス M-215, アロニックス M-220, アロニックス M-225, アロニックス M-270, アロニックス M-240, アロニックス M-6100, アロニックス M-6250, アロニックス M-6500, アロニックス M-6200, アロニックス M-309, アロニックス M-310, アロニックス M-321, アロニックス M-350, アロニックス M-360, アロニックス M-313, アロニックス M-315, アロニックス M-306, アロニックス M-303, アロニックス M-306, and the like, アロニックス M-452, アロニックス M-408, アロニックス M-403, アロニックス M-400, アロニックス M-402, アロニックス M-405, アロニックス M-406, アロニックス M-450, アロニックス M-460, アロニックス M-510, アロニックス M-520, アロニックス M-1100, アロニックス M-1200, アロニックス M-6100, アロニックス M-6200, アロニックス M-6250, アロニックス M-6500, アロニックス M-7100, アロニックス M8030, アロニックス M8060, アロニックス M8100, アロニックス M8530, アロニックス M-8560, 464M 8100, アロニックス M9050 (manufactured by Toyo Seiya Kagaku Co., Ltd.); ビスコート 295, ビスコート 300, ビスコート 360, ビスコート GPT, ビスコート 3PA, ビスコート 400, ビスコート 260, ビスコート 312, ビスコート 335HP, ビスコート 700 (manufactured by Osaka organic chemical industries, Ltd.); a-200, A-400, A-600, A-1000, AB1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701A, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (manufactured by Mitsukamura chemical industries, Ltd.); ライトエステル EG, ライトエステル 2EG, ライトエステル 3EG, ライトエステル 4EG, ライトエステル 9EG, ライトエステル 14EG, ライトエステル 1.4BG, ライトエステル NP, ライトエステル 1.6.6 HX, ライトエステル 1.9.9 ND, ライトエステル G-101P, ライトエステル G-201P, ライトエステル DCP-M, ライトエステル BP-2EMK, ライトエステル BP-4EM, ライトエステル BP-6EM, ライトエステル TMP, ライトアクリレート 3EG-A, ライトアクリレート 4EG-A, ライトアクリレート 9EG-A, ライトアクリレート 14EG-A, ライトアクリレート PTMG-250, PTMG-1, and, ライトアクリレート NP-A, ライトアクリレート MPD-A, ライトアクリレート 1.6.6 HX-A, ライトアクリレート 1.9.9 ND-A, ライトアクリレート MOD-A, ライトアクリレート DCP-A, ライトアクリレート BP-4PA, ライトアクリレート BA-134, ライトアクリレート BP-10EA, ライトアクリレート HPP-A, ライトアクリレート G-201P, ライトアクリレート TMP-A, ライトアクリレート TMP-3EO-A, ライトアクリレート TMP-6EO-3A, ライトアクリレート PE-3A, ライトアクリレート PE-4A, B, C, E, B, C, ライトアクリレート DPE-6A, エポキシエステル 40EM, エポキシエステル 70PA, エポキシエステル 200PA, エポキシエステル 80MFA, エポキシエステル 3002M, エポキシエステル 3002A, エポキシエステル 3000MK, エポキシエステル 3000A, エポキシエステル EX-0205, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha chemical Co., Ltd.); EBECRYL (registered trademark) TPGDA, EBECRYL 145, EBECRYL 150, EBECRYL PEG400DA, EBECRYL 11, EBECRYL HPNDA, EBECRYL PEIA, EBECRYL PERA, EBECRYL TMPTA, EBECRYL TMPEOTA, EBECRYL OTA480, EBECRYL DPHA, EBECRYL 180, EBECRYL 40, EBECRYL 140, EBECRYL 204, EBECRYL 205, EBECRYL 210, EBECRYL 215, EBECRYL 220, EBECRYL 6202, EBECRYL 230, EBECRRRRYL 244, EBECRYL 245, EBECRYL 264, EBECRYL 265, EBECRRRYL 270, EBECRYL 280/15IB 284, EBECRYL 285, EBECRYL 294/25, EBECRYL 9, EBECRYL 78, EBECRYL 84RYL 8435, EBECRYL 84RYL 8435, EBECRYL GCRYL 8435, EBECRYL GCRYL 84RYL 8435, EBECRYL GCRYL 8435, EBECRYL GCRYL GC, EBECRYL 800, EBECRYL 810, EBECRYL 811, EBECRYL 812, EBECRYL 1830, EBECRYL 846, EBECRYL 851, EBECRYL 852, EBECRYL 853, EBECRYL 1870, EBECRYL 884, EBECRYL 885, EBECRYL 600, EBECRYL 605, EBECRYL 645, EBECRYL 648, EBECRYL 860, EBECRYL 1606, EBECRYL 3500, EBECRYL 3608, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 6040 (manufactured by ダイセル & オルネクス strain); SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, CD9043, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041 (manufactured by Sartomer corporation).
(B) The crosslinkable compound of component (A) is used in combination of 2 or more. The combination of 2 or more is preferably a crosslinkable compound having 2 polymerizable groups in 1 molecule and a crosslinkable compound having 3 or more polymerizable groups in 1 molecule. The crosslinkable compound having 3 or more polymerizable groups in 1 molecule may be a combination of 2 or more crosslinkable compounds having different numbers of polymerizable groups. The polymerizable group is preferably an acryloyloxy group or a methacryloyloxy group.
The content of the component (B) in the negative photosensitive resin composition of the present invention is 80 to 90% by mass with respect to 100% by mass of the component (a).
< ingredient (C) >
The component (C) in the negative photosensitive resin composition of the present invention is at least 1 kind of photopolymerization initiator. (C) The photopolymerization initiator of the component (a) is not particularly limited as long as it absorbs light from a light source used for curing light.
Examples of the photopolymerization initiator include t-butylperoxy isobutyrate, 2, 5-dimethyl-2, 5-bis (benzoyldioxy) hexane, 1, 4-bis [ α - (t-butyldioxy) -isopropoxy ] benzene, di-t-butylperoxide, 2, 5-dimethyl-2, 5-bis (t-butyldioxy) hexene hydroperoxide, α - (isopropylphenyl) -isopropyl hydroperoxide, t-butylhydroperoxide, 1-bis (t-butyldioxy) -3,3, 5-trimethylcyclohexane, butyl-4, 4-bis (t-butyldioxy) valerate, cyclohexanone peroxide, 2 ', 5, 5' -tetrakis (t-butylperoxycarbonyl) benzophenone, and, Organic peroxides such as 3,3 ', 4, 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-amylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (t-butylperoxycarbonyl) -4, 4' -dicarboxybenzophenone, t-butylperoxybenzoate, and di-t-butyldiperoxylisophthalate; quinones such as 9, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1, 2-benzoanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α -methylbenzoin, and α -phenylbenzoin; 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) benzyl } -phenyl ] -2-methyl-propan-1-one, methyl benzoylformate, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and mixtures thereof, Alkylbenzene-based compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; acylphosphine oxide-based compounds such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide; oxime ester compounds such as 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione and 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone.
The photopolymerization initiator is commercially available, and examples thereof include OMNIRAD (registered trademark) 651, OMNIRAD 184, OMNIRAD 500, OMNIRAD 2959, OMNIRAD 127, OMNIRAD 754, OMNIRAD 907, OMNIRAD 369, OMNIRAD 379EG, OMNIRAD 819, OMNIRAD 1700, OMNIRAD 1870, OMNIRAD 784, OMNIRAD 1173, OMRAD MBF, OMNIRAD 4265, OMNIRAD TPO (see above, manufactured by IGM Resins Co.) [ old IRGACURE (registered trademark) 651, IRGARE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 754, IRGACURE 907, IRGARE 631800, IRGAIRGAIRGAIRGARE, IRGAIRGAIRGAIRGAIRGAIRGARE 9, IRGACURE 819, IRGAIRGAIRGAIRGAIRRE 4265, GAIRGAIRGAIRCURE 35IRCURE 379, GAIRGAIRGAIRGAIRRE 4265, GAIRGAIRGAIRRE strain (see above, GAIRGAIRGAIRRARE) 4235, GAIRGAIRGAIRGAIRRAD 379, GAIRGAIRRARE strain (see above, GAIRGAIRGAIRGAIRRARE) 4235, GAIRGAIRGAIRGAIRGAIRGAIRGAIRGAIRRARE), GAIRGAIRRARE 4235, GAIRGAIRGAIRGAIRGAIRRARE strain, GAIRGAIRGAIRGAIRRARE 4235, GAIRGAIRGAIRGAIR, KAYACURE MBP, KAYACURE DMBI, KAYACURE EPA, KAYACURE OA (manufactured by KAYAKAYAKU KOKAI Co., LTD, supra), VICURE-10, VICURE-55 (manufactured by STAUFFER Co., LTD, supra), ESACURE (registered trademark) KIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB3, トリアジン -PMS, トリアジン A, トリアジン B (manufactured by DKSH ジャパン, supra), アデカオプトマー N-1717, アデカオプトマー N-1414, アデカオプトマー N-1606 (manufactured by ADEKA, Inc.).
(C) The photopolymerization initiator of component (A) may be used alone in 1 kind or in combination of 2 or more kinds.
The content of the component (C) in the negative photosensitive resin composition of the present invention is 3 to 20% by mass based on 100% by mass of the total amount of the component (B).
< solvent >
The negative photosensitive resin composition of the present invention includes a solvent. The solvent is not particularly limited as long as it dissolves the above-mentioned component (A), component (B) and component (C).
Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, methyl acetate, and the like, Ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, gamma-butyrolactone.
Among the above solvents, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate, and cyclohexanone are preferable from the viewpoint of improving the leveling property of the coating film.
The above solvents may be used alone in 1 kind or in combination of 2 or more kinds.
< surfactant >
The negative photosensitive resin composition of the present invention may contain a surfactant for the purpose of improving coatability. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate, nonionic sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, and the like The surfactant system, エフトップ (registered trademark) EF301, エフトップ EF303, エフトップ EF352 (manufactured by Mitsubishi マテリアル electronic conversion Co., Ltd.), メガファック (registered trademark) F-171, メガファック F-173, メガファック R-30, メガファック R-40, メガファック R-40-LM (manufactured by DIC Co., Ltd.), フロラード FC430, フロラード FC431 (manufactured by ス リ ー エ ム ジャパン Co., Ltd.), アサヒガード (registered trademark) AG710, サーフロン (registered trademark) S-382, サーフロン SC101, サーフロン SC102, サーフロン SC103, サーフロン SC104, サーフロン SC105, サーフロン SC106 (manufactured by AGC Co., Ltd.), FTX-206D, FTX-212D, Fluorine-based surfactants such as フタージェント series (available from ネオス, Ltd.) including FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, and organosiloxane polymer KP341 available from shin-Etsu chemical industry (available from Ltd.).
The surfactant may be used alone in 1 kind or in combination of 2 or more kinds. In addition, when the surfactant is used, the content of the negative photosensitive resin composition of the present invention is 3% by mass or less, for example, 0.0001% by mass to 3% by mass, preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass, based on the content of the solid content of the composition.
< other additives >
The negative photosensitive resin composition of the present invention may contain, as other additives, a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion promoter, or a dissolution accelerator such as a polyhydric phenol or a polycarboxylic acid, as necessary, as long as the effects of the present invention are not impaired.
< method for preparing composition >
The method for preparing the negative photosensitive resin composition of the present invention is not particularly limited, and for example, a method in which the alkali-soluble polymer of the component (a) is dissolved in the solvent, and the crosslinkable compound of the component (B) and the photopolymerization initiator of the component (C) are mixed in a predetermined ratio in the obtained solution to prepare a uniform solution can be mentioned. Further, there may be mentioned a method of adding and mixing the above-mentioned other additives as necessary at an appropriate stage of the preparation method.
< use of negative photosensitive resin composition >
The negative photosensitive resin composition of the present invention is applied to a substrate [ for example, a semiconductor substrate such as silicon coated with a silicon oxide film, a semiconductor substrate such as silicon coated with a silicon nitride film or a silicon nitride oxide film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), and a glass substrate on which an Indium Tin Oxide (ITO) film is formed ] by an appropriate application method such as a spin coater or a coater, and then prebaked using a heating device such as an electric hot plate, thereby forming a coating film.
The prebaking conditions are appropriately selected from the group consisting of a baking temperature of 80 to 150 ℃ and a baking time of 0.3 to 60 minutes, and preferably a baking temperature of 80 to 100 ℃ and a baking time of 0.5 to 5 minutes.
The film thickness of the film formed from the negative photosensitive resin composition of the present invention is, for example, 0.005 to 20 μm, preferably 0.01 to 15 μm.
Next, the obtained film is exposed to light through a mask (reticle) for forming a predetermined pattern. For the exposure, for example, g-ray, i-ray, KrF excimer laser can be used. After Exposure, Post Exposure heat (Post Exposure Bake) is performed as necessary. The conditions for heating after exposure are appropriately selected from the heating temperature of 80 to 100 ℃ and the heating time of 0.3 to 60 minutes. Further, development was performed with an alkaline developer.
Examples of the alkaline developing solution include alkaline aqueous solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine. Further, a surfactant may be added to these developers.
The developing conditions are appropriately selected from a developing temperature of 5 to 50 ℃ and a developing time of 10 to 300 seconds. The film formed from the negative photosensitive resin composition of the present invention can be easily developed at room temperature using an aqueous tetramethylammonium hydroxide solution. After development, rinsing is appropriately performed using, for example, ultrapure water as a rinsing liquid.
Then, the developed film is subjected to full-surface exposure using, for example, g-ray, i-ray or KrF excimer laser. Further, the developed film may be subjected to post-baking using a heating device such as a hot plate before or after the entire surface exposure. The post-baking conditions are suitably selected from, for example, a baking temperature of 80 to 100 ℃ and a baking time of 0.5 to 60 minutes.
Examples
The present invention will be described in more detail below with reference to synthetic examples and examples, but the present invention is not limited to the following examples.
[ measurement of weight average molecular weight ]
The device comprises the following steps: GPC System manufactured by Nippon spectral Co., Ltd
Column: shodex [ registered trademark ] GPC KF-804L and GPC KF-803L
Column oven: 40 deg.C
Flow rate: 1 ml/min
Eluent: tetrahydrofuran (THF)
Standard sample: polystyrene
[ Synthesis example 1]
After 60g of methacrylic acid, 240g of methyl methacrylate, and 7.6g of 2, 2' -azobisisobutyronitrile were dissolved in 132g of propylene glycol monomethyl ether, the solution was added dropwise over 3 hours to a flask in which 440g of propylene glycol monomethyl ether was kept at 70 ℃. After completion of the dropwise addition, the reaction was carried out for 18 hours, thereby obtaining a solution (solid content concentration: 35% by mass) of an alkali-soluble polymer (copolymer) having a structural unit represented by the following formula (1b-1) and a structural unit represented by the following formula (2 a-1). The weight average molecular weight Mw of the obtained copolymer was 35,000 (polystyrene equivalent).
Figure BDA0002953450740000171
[ Synthesis example 2]
After dissolving 61g of methacrylic acid, 122g of methyl methacrylate, 122g of styrene, and 7.6g of 2, 2' -azobisisobutyronitrile in 134g of propylene glycol monomethyl ether, the solution was added dropwise over 3 hours to a flask in which 446g of propylene glycol monomethyl ether was kept at 70 ℃. After completion of the dropwise addition, the reaction was carried out for 18 hours, whereby a solution (solid content concentration: 35% by mass) of an alkali-soluble polymer (terpolymer) having a structural unit represented by the following formula (1b-1), a structural unit represented by the following formula (2a-1) and a structural unit represented by the following formula (2b-1) was obtained. The weight average molecular weight Mw of the obtained copolymer was 35,000 (polystyrene equivalent).
Figure BDA0002953450740000172
[ example 1]
19.7g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 3.4g of PET-30 (manufactured by Nippon chemical Co., Ltd.) and 2.1g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.21g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン (Co., Ltd.)) and 0.62g of OMNIRAD (registered trademark) 184 (manufactured by IGM Resins Co., Ltd.) [ old IRGACURE (registered trademark) 184 (manufactured by BASF ジャパン (Co., Ltd.) ] as the component (C)) and 0.0040g of DFX-18 (manufactured by ネオス (Co., Ltd.) as the surfactant were dissolved in 5.6g of propylene glycol monomethyl ether and 18.4g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition.
[ example 2]
19.6g of a solution (solid content concentration: 35 mass%) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 4.1g of PET-30 (manufactured by Nippon Chemicals Co., Ltd.) and 2.1g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.21g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン Co., Ltd.) as the photopolymerization initiator as the component (C), and 0.0040g of DFX-18 (manufactured by ネオス Co., Ltd.) as the surfactant were dissolved in 5.6g of propylene glycol monomethyl ether and 18.4g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition.
[ example 3]
18.8g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 3.9g of PET-30 (manufactured by Nippon chemical Co., Ltd.) and 2.0g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.20g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン (Co., Ltd.)) and 0.59g of OMNIRAD (registered trademark) 184 (manufactured by IGM Resins Co., Ltd.) [ old IRGACURE (registered trademark) 184 (manufactured by BASF ジャパン (Co., Ltd.) ] as the component (C)) and 0.0040g of DFX-18 (manufactured by ネオス (Co., Ltd.) as the surfactant were dissolved in 6.2g of propylene glycol monomethyl ether and 18.4g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition.
[ example 4]
23.7g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 2, 5.0g of PET-30 (manufactured by Nippon chemical Co., Ltd.) and 2.5g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.25g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン (Co., Ltd.)) and 0.75g of OMNIRAD (registered trademark) 184 (manufactured by IGM Resins Co., Ltd.) [ old IRGACURE (registered trademark) 184 (manufactured by BASF ジャパン (Co., Ltd.) ] as the component (C)) and 0.0050g of DFX-18 (manufactured by ネオス (Co., Ltd.) as the surfactant were dissolved in 1.2g of propylene glycol monomethyl ether and 16.6g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition.
Comparative example 1
20.8g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 2.9g of PET-30 (manufactured by Nippon chemical Co., Ltd.) and 2.2g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.22g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン (manufactured by Co., Ltd.) and 0.65g of OMNIRAD (registered trademark) 184 (manufactured by IGM Resins Co., Ltd.) [ old IRGACURE (registered trademark) 184 (manufactured by BASF ジャパン (manufactured Co., Ltd.) ] as the component (C)) and 0.0040g of DFX-18 (manufactured by ネオス (manufactured by Co., Ltd.) as the surfactant were dissolved in 4.9g of propylene glycol monomethyl ether and 18.4g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of the present comparative example is outside the range of the present invention.
Comparative example 2
15.6g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 3.3g of PET-30 (manufactured by Nippon Chemicals Co., Ltd.) and 3.3g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 1.3g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン Co., Ltd.) as the photopolymerization initiator as the component (C), and 0.0040g of DFX-18 (manufactured by ネオス Co., Ltd.) as the surfactant were dissolved in 8.3g of propylene glycol monomethyl ether and 18.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of the present comparative example is outside the range of the present invention.
Comparative example 3
24.5g of a solution (solid content concentration: 35 mass%) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 4.3g of PET-30 (manufactured by Nippon Chemicals, Ltd.) as a crosslinkable compound as the component (B), 0.13g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン, Ltd.) as the photopolymerization initiator as the component (C), and 0.0039g of DFX-18 (manufactured by ネオス, Ltd.) as the surfactant were dissolved in 2.6g of propylene glycol monomethyl ether and 18.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) of the negative photosensitive resin composition of the present comparative example is out of the range of the present invention, and the component (B) does not contain a crosslinkable compound having 2 polymerizable groups in 1 molecule.
Comparative example 4
23.2g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 4.1g of PET-30 (manufactured by Nippon Chemicals, Ltd.) as a crosslinkable compound as the component (B), 0.8g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン, Ltd.) as the photopolymerization initiator as the component (C), and 0.0039g of DFX-18 (manufactured by ネオス, Ltd.) as the surfactant were dissolved in 3.4g of propylene glycol monomethyl ether and 18.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) of the negative photosensitive resin composition of the present comparative example is out of the range of the present invention, and the component (B) does not contain a crosslinkable compound having 2 polymerizable groups in 1 molecule.
Comparative example 5
19.5g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 4.1g of PET-30 (manufactured by Nippon Chemicals Co., Ltd.) and 2.0g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 0.061g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン Co., Ltd.) as the photopolymerization initiator as the component (C), and 0.0039g of DFX-18 (manufactured by ネオス Co., Ltd.) as the surfactant were dissolved in 5.9g of propylene glycol monomethyl ether and 18.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (C) in the negative photosensitive resin composition of the comparative example is out of the range of the present invention.
Comparative example 6
17.1g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 1, 3.6g of PET-30 (manufactured by Nippon Chemicals Co., Ltd.) and 1.8g of ABE-300 (manufactured by New Zhongcun chemical industry Co., Ltd.) as the crosslinkable compound as the component (B), 1.6g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン Co., Ltd.) as the photopolymerization initiator as the component (C), and 0.0039g of DFX-18 (manufactured by ネオス Co., Ltd.) as the surfactant were dissolved in 7.4g of propylene glycol monomethyl ether and 18.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (C) in the negative photosensitive resin composition of the comparative example is out of the range of the present invention.
Comparative example 7
24.9g of a solution (solid content concentration: 35% by mass) of the alkali-soluble polymer as the component (A) obtained in Synthesis example 2, 5.3g of PET-30 (manufactured by Nippon Chemicals, Inc.) as the crosslinkable compound as the component (B), 0.26g of IRGACURE (registered trademark) OXE01 (manufactured by BASF ジャパン, Inc.) and OMNIRAD (registered trademark) 184 (manufactured by IGM Resins, Inc.) [ 0.78g of old IRGACURE (registered trademark) 184 (manufactured by BASF ジャパン, Inc.) ] as the component (C), and 0.0045g of DFX-18 (manufactured by ネオス, Inc.) as the surfactant were dissolved in 1.3g of propylene glycol monomethyl ether and 17.5g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the mixture was filtered through a polyethylene microfilter having a pore size of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) of the negative photosensitive resin composition of the present comparative example is out of the range of the present invention, and the component (B) does not contain a crosslinkable compound having 2 polymerizable groups in 1 molecule.
[ measurement of transmittance ]
The negative photosensitive resin compositions prepared in examples 1 to4 and comparative examples 1 to 7 were coated on a quartz substrate using a spin coater, and were prebaked on a hot plate at 100 ℃ for 90 seconds, thereby forming resin films having thicknesses shown in table 1. Next, the irradiation amount at 365nm was set to 1000mJ/cm by an ultraviolet irradiation apparatus PLA-501(F) (manufactured by キヤノン Co.)2The entire surface of the resin film is irradiated with ultraviolet rays. Then, the above resin film was post-baked on a hot plate at 100 ℃ for 5 minutes. Further, the exposure amount at 365nm was set to 1000mJ/cm by using a batch UV irradiation apparatus (high pressure mercury lamp, 2 kW. times.1 lamp) (manufactured by アイグラフィックス Co., Ltd.)2The cured film is formed on the quartz substrate by irradiating the entire surface of the resin film with ultraviolet rays. Both the pre-bake and post-bake are carried out in the atmosphere. For these cured films, UV-visible light was usedThe transmittance was measured by changing the wavelength of a spectrophotometer UV-2550 (manufactured by Shimadzu corporation) by 2nm in a wavelength range of 400nm to 800 nm. The values of the minimum transmittance measured at a wavelength of 400nm to 800nm are shown in Table 2. It is shown that the closer the value is to 100%, the more transparent the film can be obtained.
[ solvent resistance test ]
The negative photosensitive resin compositions prepared in examples 1 to4 and comparative examples 1 to 7 were coated on a silicon wafer using a spin coater, and prebaked on a hot plate at 100 ℃ for 90 seconds, to form resin films having the film thicknesses shown in table 1. Next, the irradiation amount at 365nm was set to 1000mJ/cm by an ultraviolet irradiation apparatus PLA-501(F) (manufactured by キヤノン Co.)2The entire surface of the resin film is irradiated with ultraviolet rays. Then, the resin film was developed for 60 seconds using a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration shown in table 1 as an alkaline developer, and washed with ultrapure water for 20 seconds, followed by drying. As a result, the resin film formed from the negative photosensitive resin compositions prepared in comparative examples 3 and 5 was removed from the silicon wafer. Further, the remaining resin film was post-baked on a hot plate at 100 ℃ for 5 minutes. Finally, the exposure amount at 365nm was adjusted to 1000mJ/cm by using a batch UV irradiation apparatus (high pressure mercury lamp, 2 kW. times.1 lamp) (manufactured by アイグラフィックス Co., Ltd.)2The entire surface of the resin film is irradiated with ultraviolet rays, thereby forming a cured film on the silicon wafer. Both the pre-bake and post-bake are carried out in the atmosphere. These cured films were immersed in an aqueous solution of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl 3-methoxypropionate, and 2.38 mass% tetramethylammonium hydroxide (TMAH) at a temperature of 23 ℃ for 2 minutes. The change in film thickness of the cured film was measured before and after immersion. Even if 1 of the above solvents used in the immersion test had an increase or decrease in film thickness of 10% or more with respect to the film thickness of the cured film before immersion, the test was described as "x", and the test was described as "Δ" when the test had an increase or decrease in film thickness of less than 10% and 5% or more, and the test was described as to all solventsOn the other hand, the increase and decrease in film thickness were all less than 5%, and the film thickness was marked as ". smallcircle" and the film thickness was marked as "-" when the film thickness could not be measured, and the solvent resistance was evaluated. The evaluation results are shown in table 2.
[ residual film ratio, sensitivity and residue evaluation ]
The negative photosensitive resin compositions prepared in examples 1 to4 and comparative examples 1 to 7 were coated on a silicon wafer using a spin coater, and prebaked on a hot plate at 100 ℃ for 90 seconds, to form resin films having the film thicknesses shown in table 1. The prebaking described above is carried out in the atmosphere. The film thickness of these resin films was measured using an optical interference type film thickness measuring apparatus ラムダエース VM-2110 (manufactured by SCREEN セミコンダクターソリューションズ Co., Ltd.). Next, the resin film was exposed to light through a binary mask by an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by ニコン). Then, the resin film was developed for 60 seconds using a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration shown in table 1 as an alkaline developer, and washed with ultrapure water for 20 seconds, followed by drying. As a result, a rectangular pattern of 7mm × 7mm was formed on the silicon wafer from the resin film formed from the negative photosensitive resin composition prepared in examples 1 to4, comparative example 1, comparative example 2, comparative example 4, comparative example 6, and comparative example 7. On the other hand, the rectangular pattern was not formed from the resin film formed from the negative photosensitive resin composition prepared in comparative examples 3 and 5. The thickness of the film formed on the silicon wafer was measured by the same method as that for the film thickness of the resin film. The residual film ratio (%) was evaluated as compared with the film thickness of the resin film immediately after the prebaking. The results are shown in table 2. The residual film ratio is preferably calculated by the formula (film thickness after development/film thickness after prebaking) × 100, and the more the numerical value is close to 100%, the more the exposed portion of the resin film is not easily dissolved in the developer.
Further, the minimum exposure amount at which the residual film ratio becomes maximum was evaluated. The results are shown in table 2. Even if the exposure amount is 800mJ/cm2In the case where the above residual film ratio is not maximized, or in the case where a rectangular pattern of 7mm × 7mm is not formed, the following meansFor the purpose of being unable to be measured, is expressed as "-". The smaller the minimum exposure amount is shown, the higher the sensitivity of the above resin film.
Further, the film thickness of the unexposed portion of the resin film was measured using an optical interference type film thickness measuring apparatus ラムダエース VM-2110 (manufactured by SCREEN セミコンダクターソリューションズ, Inc.). It is shown that the thinner the film thickness, the less the residue. The film thickness was marked as "X" when it was 10nm or more, as "Delta" when it was less than 10nm and 5nm or more, and as "O" when it was less than 5nm, and the residue was evaluated. The evaluation results are shown in table 2.
[ Table 1]
TABLE 1
Figure BDA0002953450740000241
[ Table 2]
TABLE 2
Figure BDA0002953450740000251

Claims (7)

1. A negative photosensitive resin composition comprising a component (A), a component (B) which is 80 to 90 mass% relative to 100 mass% of the component (A), a component (C) which is 3 to 20 mass% relative to 100 mass% of the total amount of the component (B), and a solvent,
(A) the components: a polymer which is alkali-soluble,
(B) the components: 1 at least 2 kinds of crosslinkable compounds having 2 or more polymerizable groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group and a vinyl group in a molecule,
(C) the components: at least 1 photopolymerization initiator.
2. The negative photosensitive resin composition according to claim 1, wherein the at least 2 kinds of crosslinkable compounds include a crosslinkable compound having 1 molecule having 2 acryloyloxy groups or methacryloyloxy groups as the polymerizable groups, and a crosslinkable compound having 1 molecule having 3 or more acryloyloxy groups or methacryloyloxy groups as the polymerizable groups.
3. The negative photosensitive resin composition according to claim 1 or 2, the alkali-soluble polymer having a structural unit selected from the group consisting of the following formula (1a), formula (1b), formula (1c), formula (1d), and formula (1e),
Figure FDA0002953450730000011
in the formula, R1Represents a hydrogen atom or a methyl group, A represents an-O-group or an-NH-group, X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or a divalent linking group containing an alkyleneoxy group having 1 to 3 carbon atoms, and Z1Represents hydroxyphenyl or carboxyphenyl, Z2Represents hydroxyphenyl, carboxyphenyl or carboxyl, Z3Represents a hydrogen atom, a hydroxyphenyl group or a carboxyphenyl group.
4. The negative photosensitive resin composition according to claim 3, wherein the alkali-soluble polymer is a copolymer further having a structural unit different from the structural unit and selected from the following formulae (2a), (2b) and (2c),
Figure FDA0002953450730000021
in the formula, R1A and X have the same meanings as defined in claim 3, and Z is4Represents a linear organic group having 1 to 3 carbon atoms or a branched or cyclic organic group having 3 to 14 carbon atoms.
5. The negative photosensitive resin composition according to any one of claims 1 to4, which is used for forming a microlens.
6. A method for manufacturing a microlens, comprising the steps of: a step of forming a resin film by applying the negative photosensitive resin composition according to claim 5 onto a substrate and prebaking the composition; exposing the resin film through a mask; developing the exposed resin film with an alkaline developer; and exposing the entire surface of the developed resin film.
7. The method of manufacturing a microlens according to claim 6, further comprising a step of post-baking the resin film after or before the step of exposing the entire surface of the developed resin film.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007140174A (en) * 2005-11-18 2007-06-07 Fujifilm Corp Pattern forming material, and pattern forming apparatus and pattern forming method
CN101171550A (en) * 2005-05-12 2008-04-30 东京应化工业株式会社 Method for enhancing optical stability of three-dimensional micromolded product
JP2010020077A (en) * 2008-07-10 2010-01-28 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition for forming microlens protection film, photosensitive dry film for forming microlens protection film, and liquid crystal display device
JP2011002655A (en) * 2009-06-18 2011-01-06 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element and method for producing microlens array
JP2011202025A (en) * 2010-03-25 2011-10-13 Fujifilm Corp Solid dispersion, colored photosensitive composition, inkjet ink, color filter and method for manufacturing the same, solid imaging element, display, metal complex compound, and its tautomer
JP2014002285A (en) * 2012-06-19 2014-01-09 Hitachi Chemical Co Ltd Barrier rib forming material, photosensitive element using the same, method for forming barrier rib and method of manufacturing image display device
CN105765458A (en) * 2013-10-21 2016-07-13 日产化学工业株式会社 Negative photosensitive resin composition

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2776810B2 (en) 1987-07-03 1998-07-16 ソニー株式会社 Method for manufacturing solid-state imaging device
JP3254759B2 (en) 1992-09-25 2002-02-12 ソニー株式会社 Method of manufacturing optical element and on-chip lens
JP4749760B2 (en) 2005-05-12 2011-08-17 東京応化工業株式会社 Manufacturing method of three-dimensional micro-molded body
JP2007249190A (en) 2006-02-14 2007-09-27 Fujifilm Electronic Materials Co Ltd Photocurable composition, antireflection film using the same, and solid imaging element
JP2009216727A (en) 2008-03-06 2009-09-24 Sumitomo Chemical Co Ltd Microlens and photosensitive composition for microlens
JP5555415B2 (en) * 2008-09-30 2014-07-23 富士フイルム株式会社 Curable coloring composition and method for producing the same, color filter, and solid-state imaging device
US8722311B2 (en) 2010-01-26 2014-05-13 Nissan Chemical Industries, Ltd. Positive resist composition and method for producing microlens
KR101740473B1 (en) 2011-01-31 2017-05-26 닛산 가가쿠 고교 가부시키 가이샤 Photosensitive resin composition for formation of microlenses
WO2017141723A1 (en) * 2016-02-19 2017-08-24 富士フイルム株式会社 Curable composition, light-shielding film, solid-state imaging device, and color filter
JP6744233B2 (en) * 2017-01-30 2020-08-19 日本化薬株式会社 Polyurethane compound, active energy ray-curable resin composition containing the same and use thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101171550A (en) * 2005-05-12 2008-04-30 东京应化工业株式会社 Method for enhancing optical stability of three-dimensional micromolded product
JP2007140174A (en) * 2005-11-18 2007-06-07 Fujifilm Corp Pattern forming material, and pattern forming apparatus and pattern forming method
JP2010020077A (en) * 2008-07-10 2010-01-28 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition for forming microlens protection film, photosensitive dry film for forming microlens protection film, and liquid crystal display device
JP2011002655A (en) * 2009-06-18 2011-01-06 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element and method for producing microlens array
JP2011202025A (en) * 2010-03-25 2011-10-13 Fujifilm Corp Solid dispersion, colored photosensitive composition, inkjet ink, color filter and method for manufacturing the same, solid imaging element, display, metal complex compound, and its tautomer
JP2014002285A (en) * 2012-06-19 2014-01-09 Hitachi Chemical Co Ltd Barrier rib forming material, photosensitive element using the same, method for forming barrier rib and method of manufacturing image display device
CN105765458A (en) * 2013-10-21 2016-07-13 日产化学工业株式会社 Negative photosensitive resin composition

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