JP7413762B2 - Curable resin composition and cured film - Google Patents

Description

The present invention relates to a curable resin composition used for forming a film on an upper or lower layer of a color filter or the like.

In recent years, development and mass production of display devices using organic EL (organic electroluminescence), which is a self-emitting element, has been progressing in electronic devices such as mobile information terminals. Additionally, with the spread of camera-equipped mobile phones, demand for solid-state image sensors is increasing. Color filters are used as these key devices.

These devices are provided with a protective film (overcoat film) to prevent deterioration or damage to the color filter, and a flattening film to flatten the element surface of the upper and lower layers on which the color filter is provided. For example, Patent Document 1 discloses a curable resin composition containing a silane coupling agent, an alkali-soluble resin, a bifunctional or higher polyfunctional (meth)acrylate compound, and a photopolymerization initiator.

Japanese Patent Application Publication No. 2015-030732

When a curable resin composition is used for a device that has low heat resistance and cannot be processed at high temperatures, it is often formed into a film at a low temperature of 80° C. or lower. However, the silane coupling agent contained in the conventional curable resin composition has a problem in that it is difficult to obtain desired adhesion because the dehydration reaction becomes difficult to proceed when the heating temperature becomes low. Furthermore, the silane coupling agent tends to react with moisture in the composition, resulting in a problem of lowering the storage stability of the composition.

The present invention aims to provide a curable resin composition and a cured film that have excellent adhesion when heated at low temperatures and excellent storage stability.

The curable resin composition of the present invention contains a basic resin (A), an alkali-soluble resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator (D), and contains an organic pigment. and carbon black free.

The present invention described above can provide a curable resin composition and a cured film that have excellent adhesion when heated at low temperatures and excellent storage stability.

Define terms used herein. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". The polymerizable unsaturated group is an ethylenically unsaturated group, such as a vinyl group or a (meth)acryloyl group.

The curable resin composition of the present invention contains a basic resin (A), an alkali-soluble resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator (D), and contains an organic pigment. and carbon black free.
The curable resin composition of the present invention is preferably used to form a film on members such as color filters and base materials (also referred to as substrates) to improve adhesion and protect other members.

<Basic resin (A)>
The basic resin (A) is a resin having a basic functional group. By containing the basic resin (A), the curable resin composition not only improves adhesion to other members, but also does not impair the storage stability of the composition. In addition, the curable resin composition of this specification can contain a silane coupling agent as long as the problem can be solved.

Examples of the basic functional group include an amino group, an amide group, a urethane group, and a urea group. Among these, amino groups are preferred, and tertiary amino groups are more preferred. Examples of the resin type of the basic resin (A) include acrylic resin, amide resin, urethane resin, and urea resin. Examples of the shape of the basic resin (A) include a linear type and a graft type. Moreover, the polymerization form of the basic resin (A) includes a random copolymer, a block copolymer, and the like.

The basic resin (A) is preferably an amino group-containing acrylic resin. Thereby, for example, when the curable resin composition contains an organic solvent, the compatibility of the basic resin (A) with the organic solvent is improved. Moreover, the solvent resistance of the cured film is improved.

Examples of the monomer constituting the basic resin (A) include a basic functional group-containing monomer and other monomers.
Basic functional group-containing monomers include, for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, Diethylaminobutyl (meth)acrylate, pentamethylpiperidyl methacrylate, tetramethylpiperidyl methacrylate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Examples include (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate Acrylate, (meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate, styrene or α- Examples include styrenes such as methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

The monomers can be used alone or in combination of two or more.

Commercially available basic resins (A) include, for example, Disperbyk-101, 140, 161, 162, 163, 164, 168, 180, 182, 184, 185, 2000, 2001, 2009, manufactured by BYK Chemie Japan Co., Ltd. 2013, 2020, 2022, 2025, 2050, 2055, 2070, 2150, 2155, 2163, 2164 or BYK-9076, 9077, Anti-Terra-U, 204, SOLSPERSE-9000, 13240 manufactured by Lubrisol Japan , 13650, 13940, 17000, 18000, 20000, 24000, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35200, 38500, etc., Efka FA 4644, 4654, 4663 manufactured by BASF Japan. , Efka PA 4400, 4401 , 4403, Efka PU4063, Efka PX4300, 4310, 4320, 4330, 4340, 4700, 4701, 4731, 4732, and Ajisper-PB821, PB822, PB824, PB881 manufactured by Ajinomoto Fine Techno.

The amine value of the basic resin (A) is preferably 30 to 350 mgKOH/g, more preferably 50 to 150 mgKOH/g. An appropriate amine value further improves adhesion and storage stability.

The weight average molecular weight of the basic resin (A) is preferably 5,000 to 20,000, more preferably 8,000 to 15,000.

The content of the basic resin (A) is preferably 0.01 to 60% by mass, more preferably 0.1 to 30% by mass based on 100% by mass of nonvolatile content of the curable resin composition.

<Alkali-soluble resin (B)>
The curable resin composition of this specification contains an alkali-soluble resin (B). Alkali solubility means that when the curable resin composition is used as a base layer, the base layer is removed together with the filter segments in the non-exposed areas during the alkaline development step when producing a color filter to be formed on the base layer. It is necessary for developing solubility. Note that an acidic group is required for alkali solubility.

The alkali-soluble resin (B) is preferably a resin that has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a film with a thickness of 2 μm is formed. Note that the transmittance is preferably 95% or more. The alkali-soluble resin (B) is preferably an alkali-soluble photosensitive resin having a polymerizable unsaturated group. Note that the alkali-soluble resin (B) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

Examples of the alkali-soluble resin (non-photosensitive) include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(meth)acrylic acid copolymer. Examples include (anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred from the viewpoint of improving developability, heat resistance, and transparency.

The alkali-soluble photosensitive resin only needs to be alkali-soluble and photosensitive, and known resins can be used, but resins synthesized by the following methods (i) and (ii) are preferred. When an alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking upon irradiation with light, increasing the crosslinking density, thereby improving the chemical resistance of the coating.

[Method (i)]
In method (i), for example, first, a polymer of an epoxy group-containing monomer and other monomers is synthesized. Next, a method can be mentioned in which a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the generated hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. Note that the monocarboxyl group-containing monomer is a monomer having one carboxyl group.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylate is mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of monocarboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted α-positions of (meth)acrylic acid. Examples include monocarboxylic acids such as carboxylic acid and the like.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Note that the polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate (Meth)acrylates such as acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; ) Acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine, styrene, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate. .

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4- Phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. can be mentioned.

In method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to produce a polymer. Next, a method of synthesizing an alkali-soluble photosensitive resin by reacting an isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the polymer may be mentioned.

Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, Examples include acrylates and hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester Also included are polyester mono(meth)acrylates to which 12-hydroxystearic acid and the like are added. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

Examples of the isocyanate group-containing monomer include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

Monomers that can be used in addition to the above monomers include, in addition to the other monomers exemplified in the method (i) above, phosphate group-containing monomers.

The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphoric acid esterification agent such as phosphorus pentoxide or polyphosphoric acid.

Each raw material used in the synthesis of the alkali-soluble resin can be used alone or in combination of two or more.

The alkali-soluble resin (B) can be used alone or in combination of two or more types.

The acid value of the alkali-soluble resin (B) is preferably 30 to 130 mgKOH/g, more preferably 60 to 100 mgKOH/g. Having an appropriate acid value further improves alkali developability.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. Alkaline developability is further improved by appropriate Mw. Moreover, the value of Mw/Mn is preferably 10 or less. In addition, Mn is a number average molecular weight.

The content of the alkali-soluble resin is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on 100% by mass of nonvolatile content of the curable resin composition. When contained in an appropriate amount, a film can be easily formed and good patterning characteristics can be easily obtained.

<Thermoplastic resin>
The curable resin composition can contain a thermoplastic resin that does not have alkali solubility. This allows the developability to be adjusted as appropriate.
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

<Photopolymerizable monomer (C)>
The photopolymerizable monomer (C) includes monomers and oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins. The photopolymerizable monomer (C) is preferably a (meth)acrylate having three or more polymerizable unsaturated groups. When a (meth)acrylate having three or more polymerizable unsaturated groups is used, not only the crosslinking density of the cured film is improved, but also the solvent resistance of the cured film is improved. The upper limit of the number of polymerizable unsaturated groups is not limited as long as the problem can be solved, but it is preferably 10 or less, more preferably 6 or less.

Examples of (meth)acrylates having three or more polymerizable unsaturated groups include trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, and isocyanuric acid. EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate etc.

As the photopolymerizable monomer (C), in addition to (meth)acrylate having three or more polymerizable unsaturated groups, acid group-containing monomers, urethane bond-containing monomers, and other photopolymerizable monomers can be used. .

Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Acid group-containing monomers include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; ) Examples include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with an alcohol, and then a (meth)acrylate having a hydroxyl group. Examples include polyfunctional urethane acrylates obtained by reaction.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate , glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Other photopolymerizable monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxylate. Ethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate Acrylate, phenoxyhexaethylene glycol (meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, Examples include ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

The photopolymerizable monomer (C) can be used alone or in combination of two or more types.

The blending amount of the photopolymerizable monomer (C) is preferably 1 to 90% by weight, more preferably 10 to 85% by weight based on 100% by weight of nonvolatile content of the curable resin composition. When blended in an appropriate amount, curability and developability are further improved.

<Photopolymerization initiator (D)>
The photoinitiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexyl phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) ) phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone compounds such as butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2 - Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloro methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl) -6-triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2- (O-benzoyloxime)], or oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Compounds: Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone Examples include quinone compounds such as; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. When the cured film layer is applied as a thin film, the degree of curing of the coating film may be low because it is susceptible to curing inhibition by oxygen, but oxime ester compounds are preferably used because they have high quantum efficiency.

Oxime ester compounds include oximes described in JP-A No. 2007-210991, JP-A 2009-179619, JP-A 2010-037223, JP-A 2010-215575, JP-A 2011-020998, etc. Examples include ester photopolymerization initiators.

The photopolymerization initiator (D) can be used alone or in combination of two or more types.

The content of the photopolymerization initiator (D) is preferably 1 to 20 parts by mass, and 2 to 15 parts by mass based on a total of 100 parts by mass of the alkali-soluble resin (B) and the photopolymerizable monomer (C). More preferred. When incorporated in an appropriate amount, photocurability and resolution are further improved.

<Sensitizer>
The curable resin composition can further contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinones. derivatives, polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4' -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis( dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N - Ethylcarbazole and the like are more preferred.

The sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D). When contained in an appropriate amount, curability and developability are further improved.

<Thermosetting compound>
The curable resin composition can contain a thermosetting compound. The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

<Thiol-based chain transfer agent>
The curable resin composition can contain a thiol-based chain transfer agent. When a thiol-based chain transfer agent is used in combination with a photopolymerization initiator, thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, thereby improving the sensitivity of the curable resin composition.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). In addition, it is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photocure from the surface of the film to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-Hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine etc. Among these, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are preferred.

Thiol-based chain transfer agents can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by weight, more preferably 0.1 to 3% by weight based on 100% by weight of nonvolatile content of the curable resin composition. When contained in an appropriate amount, photosensitivity is improved and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The curable resin composition can contain a polymerization inhibitor. This prevents exposure due to diffracted light from the mask during exposure, making it easier to obtain a good pattern shape.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl Catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert - Alkylcatechol compounds such as butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-di-tert-butylhydroquinone and other alkylhydroquinone compounds, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of nonvolatile content of the curable resin composition. When contained in an appropriate amount, it becomes easier to obtain a good pattern shape.

<Ultraviolet absorber>
The curable resin composition can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. Note that the ultraviolet absorber may be an oligomer or a polymer.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -dimethylethyl)-4-hydroxy, mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3 -(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1 , 1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3 , 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3- tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5- Chloro-2H-benzotriazol-2-yl)phenyl]propionate is mentioned.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis(2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2'-di-hydroxy-4-methoxybenzophenone. , 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, Examples include 2,2',4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total of 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

In addition, the total content of the photopolymerization initiator and the ultraviolet absorber is 1 to 20 parts by mass based on the total of 100 parts by mass of the alkali-soluble resin (B) and the photopolymerizable monomer (C) of the curable resin composition. part is preferred. When contained in an appropriate amount, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

<Antioxidant>
The curable resin composition can contain an antioxidant. The antioxidant can prevent the photopolymerization initiator and thermosetting compound contained in the curable resin composition from yellowing due to oxidation during thermosetting. This can improve the transparency of the cured film.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

Antioxidants can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of nonvolatile content of the curable resin composition. This further improves transmittance and sensitivity.

<Leveling agent>
The curable resin composition can contain a leveling agent. This further improves the wettability to the transparent substrate during coating formation and the drying properties of the coating. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Leveling agents can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass based on 100% by mass of nonvolatile content of the curable resin composition. Within this range, the balance between coatability and transmittance of the curable resin composition is further improved.

<Storage stabilizer>
The curable resin composition can contain a storage stabilizer to stabilize the viscosity of the composition over time.
Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, and organic acids such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include phosphine and phosphites.

The storage stabilizer is preferably about 0.01 to 1% by mass based on 100% by mass of nonvolatile content of the curable resin composition.

<Solvent>
The curable resin composition can contain a solvent. This makes it easier to adjust the viscosity of the curable resin composition, making it easier to form a film with a smooth surface. The solvent may be appropriately selected depending on the purpose of use and may be contained in an appropriate amount.

Examples of the solvent include ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- but not -COO- in the molecule), and ether ester solvents. (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and -O -, -CO- and -COO--free), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Among these, solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferred in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, cyclohexyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl -2-pentanone, cyclohexanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexyl acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred. preferable.

The solvents can be used alone or in combination of two or more.

<Color filter>
Preferably, the color filter herein has a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter can further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment as color filter segments. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

<Method for manufacturing cured film>

The cured film can be produced by, for example, a photolithography method.
In the photolithography method, for example, a curable resin composition is applied onto a substrate to form a film with a dry film thickness of about 0.05 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Next, development is performed by immersing in a solvent or alkaline developer or spraying a developer, and uncured portions are removed to obtain a desired pattern. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved.

The cured film of this specification may be formed as a protective film on a color filter.

Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; organic alkalis such as tetramethylammonium hydroxide, dimethylbenzylamine, and triethanolamine. Further, an antifoaming agent and a surfactant can be added to the developer.

In this specification, the cured film can be used for members constituting solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, head-mounted displays, and the like.

The present invention will be described below based on Examples, but the present invention is not limited thereto. Also,
Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass." Note that Examples 4, 5, 6, and 7 are reference examples.

First, a calculation method for measuring the average molecular weight of the resin and the acid value of the resin will be explained.

(Average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40. ℃, using a tetrahydrofuran (THF) solution as an eluent, and a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use an automatic titration device ("COM-555" manufactured by Hiranuma Sangyo) using 0.1 mol/L KOH aqueous solution as the titrant. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(Amine value of basic resin (mgKOH/g))
The amine value of the basic resin is the value obtained by converting the total amine value (mgKOH/g) measured in accordance with the method of ASTM D 2074 into nonvolatile content.

<Production example of basic resin (A)>
(Production of basic resin (A-1))
In a four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, add 70 parts of methyl ethyl ketone (MEK), 80.0 parts of n-butyl methacrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate. The temperature was raised to 40°C under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75°C to start polymerization. After polymerization for 3 hours, the polymerization solution was sampled and it was confirmed that the polymerization yield was 95% or more from the nonvolatile components of the polymerization, and 20.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added. , polymerization continued. After 2 hours, it was confirmed from the nonvolatile components of the polymerization solution that the polymerization yield was 97% or more, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin "Diaion PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added, and the mixture was stirred at room temperature for 1 hour. 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.)" was added and stirred for 30 minutes. Residues of the polymerization catalyst were removed by removing the cation exchange resin and adsorbent by filtration. Furthermore, the resin solution was concentrated and replaced with propylene glycol monomethyl ether acetate to prepare a solution of a basic resin (Mw = 8700, amine value 61 mgKOH/g) (A-1) having a tertiary amino group with a nonvolatile content of 40% by weight. I got it.

(Production of basic resin (A-2))
133 parts of methoxypropyl acetate was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 100° C. while purging with nitrogen. Charge 40 parts of N,N-dimethylaminoethyl methacrylate, 160 parts of n-butyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) into a dropping tank and mix uniformly. After the mixture was stirred until the mixture was mixed, it was added dropwise to the reaction tank over 2 hours, and the reaction was continued for 3 hours at the same temperature. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by mass. A solution of a basic resin having a grade amino group (Mw=8800, amine value=61 mgKOH/g) (A-2) was obtained.

(Production of basic resin (A-3))
70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate were placed in a four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser. The temperature was raised to 40°C under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75°C to start polymerization. After 3 hours of polymerization, the polymerization solution was sampled and it was confirmed that the polymerization yield was 95% or more from the nonvolatile components of the polymerization, and 24.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added. Furthermore, polymerization was performed. After 2 hours, it was confirmed from the nonvolatile components of the polymerization solution that the polymerization yield was 97% or more, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin "Diaion PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added, and the mixture was stirred at room temperature for 1 hour. 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.)" was added and stirred for 30 minutes. Residues of the polymerization catalyst were removed by removing the cation exchange resin and adsorbent by filtration. Furthermore, the resin solution was concentrated and replaced with propylene glycol monomethyl ether acetate to obtain a solution of a basic resin (Mw = 12200, amine value 86 mgKOH/g) (A-3) having a tertiary amino group with a nonvolatile content of 40% by weight. I got it.

(Production of basic resin (A-4))
70 parts of methyl ethyl ketone, 96.0 parts of n-butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate were placed in a four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser. The temperature was raised to 40°C under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75°C to start polymerization. After 3 hours of polymerization, the polymerization solution was sampled and it was confirmed that the polymerization yield was 95% or more from the nonvolatile components of the polymerization, and 4.0 parts of N,N-dimethylamiethyl methacrylate and 30.0 parts of methyl ethyl ketone were added. Then, polymerization was further carried out. After 2 hours, it was confirmed from the nonvolatile components of the polymerization solution that the polymerization yield was 97% or more, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin "Diaion PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added, and the mixture was stirred at room temperature for 1 hour. 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.)" was added and stirred for 30 minutes. Residues of the polymerization catalyst were removed by removing the cation exchange resin and adsorbent by filtration. Furthermore, the resin solution was concentrated and replaced with propylene glycol monomethyl ether acetate to obtain a solution of a basic resin (Mw = 12000, amine value 14 mgKOH/g) (A-4) having a tertiary amino group with a nonvolatile content of 40% by weight. I got it.

(Production of basic resin (A-5))
133 parts of methoxypropyl acetate was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 100° C. while purging with nitrogen. A dropping tank was charged with 180 parts of N,N-dimethylaminoethyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and then uniformly mixed. The mixture was stirred until the mixture was dissolved, and then added dropwise to the reaction tank over a period of 2 hours.The reaction was then continued at the same temperature for 3 hours to obtain a solution of a vinyl resin having a tertiary amino group. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 40% by weight. Acetate was added to obtain a basic resin having a tertiary amino group (Mw=10000, amine value 330 mgKOH/g) (A-5) solution.

(Production of basic resin (A-6))
133 parts of propylene glycol monomethyl ether acetate (PGMAc) was charged into a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while purging with nitrogen. Charge 177 parts of diethylaminoethyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) into a dropping tank until uniform. After stirring, it was added dropwise to the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Furthermore, propylene glycol monomethyl ether acetate was added to dilute the nonvolatile content to 40% by weight, resulting in a basic resin having a tertiary amino group (Mw=9000, amine value 315 mgKOH/g) (A-6). A solution was prepared.

(Production of basic resin (A-7))
133 parts of PGMAc was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while purging with nitrogen. In a dropping tank were placed 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 2,2'-azobis(2,4-dimethylvalero). After charging 6 parts of nitrile and stirring until uniform, the mixture was added dropwise to the reaction tank over 2 hours, and the reaction was then continued at the same temperature for 3 hours. Furthermore, propylene glycol monomethyl ether acetate was added to dilute the nonvolatile content to 40% by weight, resulting in a basic resin having a tertiary amino group (Mw=7200, amine value 201mgKOH/g) (A-7). A solution was prepared.

(Adjustment of basic resin (A-8))
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the mixture was flushed with nitrogen. The mixture was stirred at 50° C. for 1 hour, and the inside of the reactor was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to start polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) were added to this reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. and nitrogen atmosphere. Two hours after adding 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was 98 in terms of non-volatile content. % or more, and the reaction solution was cooled to room temperature to stop the polymerization. Furthermore, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by weight to obtain a basic resin having a tertiary amino group (Mw=5400, amine value 57 mgKOH/g) (A-8) solution. Ta.

(Adjustment of basic resin (A-9))
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the inside of the reaction apparatus was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc as a catalyst were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B block). Polymerization started. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the mixture was kept at 110°C under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or more in terms of nonvolatile content, and the reaction solution was heated to room temperature. Polymerization was stopped by cooling. Furthermore, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40%, and a basic resin having a tertiary amino group and a quaternary ammonium base (Mw=20000, amine value 170 mgKOH/g) (A-9 ) solution was obtained.

<Production example of alkali-soluble resin (B)>
(Production of alkali-soluble resin (B-1))
Put 150 parts of PGMAc into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, heat it to 120°C while injecting nitrogen gas into the container, and add 10.0 parts of styrene from the dropping tube at the same temperature. A mixture of 32.4 parts of glycidyl methacrylate, 10.0 parts of dicyclopentanyl methacrylate, and 2.5 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 16.4 parts of acrylic acid, and the reaction was continued at 120° C. for 5 hours. Further, 29.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the nonvolatile content was 40% to prepare a resin (B-1) solution. The weight average molecular weight of the resin (B-1) having a polymerizable unsaturated group was 9600, and the acid value was 79 mgKOH/g.

(Production of alkali-soluble resin (B-2))
Put 150 parts of PGMAc into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, heat it to 120°C while injecting nitrogen gas into the container, and add 2-ethylhexyl acrylate 33 through the dropping tube at the same temperature. 0 part of glycidyl methacrylate, 1.0 part of dicyclopentanyl methacrylate, and 2.5 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 13.5 parts of acrylic acid, and the reaction was continued at 120° C. for 5 hours. Further, 24.2 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the nonvolatile content was 40%. 2) A solution was prepared. The weight average molecular weight of the resin (B-2) was 6400, and the acid value was 36 mgKOH/g.

(Production of alkali-soluble resin (B-3))
Put 145 parts of PGMAc into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, heat it to 120°C while injecting nitrogen gas into the container, and add dicyclopentanyl methacrylate from the dropping tube at the same temperature. A mixture of 20.0 parts of methacrylic acid, 108.0 parts of benzyl methacrylate, and 6.0 parts of azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, and 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were added to 125.7 parts of glycidyl methacrylate, and the reaction was continued at 120° C. for 6 hours. Furthermore, PGMAc was added so that the nonvolatile content was 40% to prepare a resin (B-3) solution having polymerizable unsaturated groups. The weight average molecular weight of the resin (B-3) was 18,500, and the acid value was 120 mgKOH/g.

(Production of alkali-soluble resin (B-4))
153.0 parts of propylene glycol monomethyl ether acetate was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, a mixture of 28.0 parts of methacrylic acid, 62.0 parts of benzyl methacrylate, 10.0 parts of dicyclopentanyl methacrylate, and 1.4 parts of 2,2'-azobisisobutyronitrile was added from a dropping tube for 2 hours. It dripped. After the dropwise addition was completed, the reaction was continued for another 3 hours, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by weight to prepare a resin (B-4) solution. Resin (B-4) had an acid value of 98 mgKOH/g and a weight average molecular weight of 17,500.

<Method for manufacturing curable resin composition>
[Example 1]
(Curable resin composition (R-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm to obtain a curable resin composition (R-1).
Basic resin (A-1: non-volatile content 40%) solution: 0.50 parts Alkali-soluble resin (B-1: non-volatile content 40%) solution: 3.00 parts Photopolymerizable monomer (C-1): 6.00 parts Photopolymerization initiator (D-1): 0.68 parts Leveling agent (E-1: nonvolatile content 1%): 1.00 parts Solvent (I-1): 88.82 parts

[Examples 2 to 28, Comparative Examples 1 to 2]
(Preparation of curable resin compositions (R-2 to R-30))
Cured film compositions (R-2 to R-30) were prepared in the same manner as in Example 1, except that the material type and mass were changed as shown in Table 1.

<Photopolymerizable monomer (C)>
・(C-1) Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [Aronix M450 (manufactured by Toagosei Co., Ltd.)]
・(C-2) Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [Aronix M402 (manufactured by Toagosei Co., Ltd.)]
・(C-3) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]
・(C-4) Trimethylolpropane EO modified triacrylate [Aronix M350 (manufactured by Toagosei Co., Ltd.)]
・(C-5) Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [Aronix M306 (manufactured by Toagosei Co., Ltd.)]

<Photopolymerization initiator (D)>

・(D-6) A mixture containing the same amounts of the following four types (D-6-1) to (D-6-4)

・(D-7) Compound with the following structure

<Leveling agent (E)>
・(E-1) A solution in which 1 part of "FZ-2122" manufactured by Toray Dow Corning was dissolved in 99 parts of PGMAc. ・(E-2) 30 parts of "Megafac F-563" manufactured by DIC Corporation was dissolved in 70 parts of PGMAc. solution

<Ultraviolet absorber (F)>
・(F-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine [TINUVIN326 (manufactured by BASF Japan)]
・(F-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN400 (manufactured by BASF Japan)]

<Polymerization inhibitor (G)>
・(G-1) Methylhydroquinone

<Silane coupling agent (H)>
・(H-1)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

<Solvent (I)>
・(I-1) PGMAc
- (I-2) (I-2-1) to (I-2-6) were mixed in the following parts by mass to obtain a solvent (I-2).
(I-2-1) PGMAc: 40 parts (I-2-2) Cyclohexanone: 40 parts (I-2-3) Ethyl 3-ethoxypropionate: 10 parts (I-2-4) Propylene glycol monomethyl ether: 10 parts (I-2-5) Cyclohexanol acetate: 10 parts (I-2-6) Dipropylene glycol methyl ether acetate: 10 parts

<Evaluation of curable resin composition>
The resulting curable resin composition was tested for resolution, alkaline developer resistance, substrate adhesion, and storage stability using the following methods. The results of the test are shown in Table 2.

(Resolution)
The curable resin composition was coated on a silicon wafer substrate with a thickness of 200 mm using a spin coater so that the thickness after drying was 0.20 μm, and dried at 100° C. for 20 minutes to obtain a substrate. Next, exposure was performed at 2000 J/m ² at a wavelength of 365 nm using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon). Exposure was performed through a photomask having a 10.0 μm square light-shielding portion. The exposed coating film was paddle developed with TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industries) for 1 minute. After paddle development, the film was rinsed with pure water using a spin shower for 20 seconds and spin-dried. The hole pattern formed by the light-shielding part was observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation) and evaluated according to the following criteria.
◎: One side of the hole pattern is 9.5 μm or more and less than 10.0 μm (very good level)
○: One side of the hole pattern is 9.0 μm or more and less than 9.5 μm (good level)
△: One side of the hole pattern is 8.0 μm or more and less than 9.0 μm (practical level)
×: One side of the hole pattern is less than 8.0 μm (level not suitable for practical use)
In addition, similarly below, ◎ and ○ are practically preferable levels, △ is a practically possible level, and × is a level that is not suitable for practical use.

(alkaline developer resistance)
The curable resin composition was spin-coated onto a glass substrate measuring 100 mm long x 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 0.20 μm, and dried at 100° C. for 20 minutes. . Next, the obtained film was exposed to 2000 mJ/cm ² using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² through a photomask in which a 400 μm square mask pattern was arranged. After developing the unexposed areas of the pattern-exposed film using 2.38% TMAH, the film was washed with pure water. Thereafter, the water droplets were blown off with high-pressure air, the substrate was naturally dried, and a post-bake treatment was performed on a hot plate at 100° C. for 20 minutes to form a cured film pattern on the glass substrate. The film thickness of the patterned portion of the glass substrate was measured. The thickness of the coating film was measured using Dektak3030 (manufactured by Nihon Shinku Gijutsu Co., Ltd.). Thereafter, the film was immersed in 2.38% TMAH for 10 minutes, the film thickness was measured again, and the film thickness change was evaluated. The evaluation ranks are as follows.
◎: Film thickness change is less than 0.5% 〇: Film thickness change is 0.5% or more and less than 1.0% △: Film thickness change is 1.0% or more and less than 5.0% ×: Film thickness change is 5.0% or more

(Substrate adhesion)
The curable resin composition was spin-coated onto a glass substrate measuring 100 mm long x 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 0.20 μm, and dried at 120° C. for 20 minutes. . Next, the dried coating film was exposed to 2000 mJ/cm ² using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² through a photomask having a 6 μm square mask pattern arranged thereon. The unexposed areas of the pattern-exposed coating film were developed using 2.38% TMAH, and then washed with pure water. Thereafter, the water droplets were blown away with high-pressure air, and the substrate was air-dried to form a cured film pattern on the glass substrate. Adhesion was evaluated by observing using an optical microscope. The evaluation criteria are as follows. Next, a test was carried out in the same manner as above, except that the drying temperature was changed to 100°C and 70°C, and evaluation was made in the same manner.
◎: No pattern peeling ○: 1-5% of the pattern peeled off △: 6-15% of the pattern peeled off ×: 16% or more of the pattern peeled off

(Storage stability)
The initial viscosity on the next day after preparing the curable resin composition and the viscosity over time after accelerated aging at 40° C. for one week were measured. From the obtained initial viscosity and aging viscosity values, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated using the following criteria.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
The measurement conditions were: 25°C, rotor No. 1. The measurement time was 3 minutes and the rotation speed was 20 rpm.
◎: Rate of change less than 3%〇: Rate of change 3% or more and less than 5% △: Rate of change 5% or more and less than 10% ×: Rate of change 10% or more

Claims (5)

A basic resin (A) (except when it is an alkali-soluble resin (B)) , an alkali-soluble resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator (D). Contains no organic pigments or carbon black,
The basic resin (A) has a tertiary amino group and has an amine value of 50 to 170 mgKOH/g,
A curable resin composition used to form a film on the upper or lower layer of a color filter . The curable resin composition according to claim 1, wherein the alkali-soluble resin (B) has an acid value of 30 to 130 mgKOH/g. The curable resin composition according to claim 1 or 2 , wherein the photopolymerizable monomer (C) is a (meth)acrylate having three or more polymerizable unsaturated groups. The curable resin composition according to any one of claims 1 to 3 , wherein the photopolymerization initiator (D) contains an oxime ester compound. A cured film formed from the curable resin composition according to any one of claims 1 to 4 .