TWI738750B - Curable resin composition and protective film - Google Patents

Abstract

The present invention is to provide a curable resin composition which comprises a curable resin, and a solvent; wherein, said solvent having a boiling point of 200℃ or above, the content of said solvent having a boiling point of 200℃ or above is 20 % by mass or more of the total mass of the solvent in the curable resin composition.

Description

Curable resin composition and cured film

The present invention relates to a curable resin composition and a cured film.

In recent liquid crystal displays, curable resin compositions have been used to form hardened films such as photo spacers or protective coatings. Japanese Patent Application Publication No. 2010-152335 describes a curable resin composition containing diethylene glycol ethyl methyl ether, 3-methoxy-1-butanol, and propylene glycol monomethyl ether as solvents.

The present invention includes the following inventions.

[1] A curable resin composition containing a curable resin and a solvent, wherein the solvent includes a solvent with a boiling point of 200°C or higher, and the content of the solvent with a boiling point of 200°C or higher is the curable 20% by mass or more of the total mass of the solvent in the resin composition.

[2] The curable resin composition as described in item [1], which contains a boiling point of 20% by mass or more of the total mass of the solvent in the curable resin composition It is a solvent above 220°C.

[3] The curable resin composition according to [1] or [2], wherein the content of the solvent having a boiling point of 200°C or higher is 20% by mass of the total mass of the solvent in the curable resin composition Above and below 80% by mass.

[4] The curable resin composition according to any one of [1] to [3], wherein the solvent having a boiling point of 200°C or higher is selected from 1,3-butanediol diacetate, 1 At least one of the group consisting of ,6-hexanediol diacetate, 1,2,3-triacetoxypropane, and triethylene glycol monobutyl ether.

[5] The curable resin composition described in any one of [1] to [4] further contains a solvent having a boiling point of 100°C or higher and less than 170°C.

[6] The curable resin composition as described in [5], wherein the solvent having a boiling point of 100°C or higher and less than 170°C is methoxybutanol, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether ethyl Ester, propylene glycol monomethyl ether propionate or ethylene glycol monomethyl ether acetate.

[7] The curable resin composition described in [5] or [6] further contains a solvent with a boiling point of 170°C or higher and less than 200°C.

[8] The curable resin composition according to [7], wherein the solvent having a boiling point of 170°C or higher and less than 200°C is diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, or 3-methoxybutyl acetate.

[9] The curable resin composition according to any one of [1] to [8], wherein the curable resin system contains a copolymer having the following structural unit: derived from The structural unit of at least one monomer in the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and is derived from having carbon It is a structural unit of a monomer having a cyclic ether structure of 2 to 4 and an ethylenically unsaturated bond.

[10] The curable resin composition according to item [9], wherein the curable resin further contains selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins At least one of them.

[11] A method for producing a cured film, comprising the steps of: applying the curable resin composition according to any one of [1] to [10] on a substrate; and applying the applied The step of heating the curable resin composition.

[12] The manufacturing method according to [11], wherein the cured film is a color filter or a protective film for a touch panel.

[13] A display device comprising the cured film obtained by the manufacturing method described in [12] above.

Figure 1 is a graph showing the surface shape (the surface shape of the colored pattern, the surface shape of the cured film) of the evaluation sample of Example 1.

Figure 2 is a graph showing the surface of the evaluation sample of Comparative Example 1 (the surface shape of the colored pattern, the surface shape of the cured film).

In this specification, unless otherwise specified, the compounds exemplified as each component can be used alone or in combination of several kinds.

The curable resin composition of the present invention contains a curable resin (hereinafter, the resin is also referred to as "resin (A)") and a solvent A curable resin composition, wherein the aforementioned solvent system contains a solvent having a boiling point of 200°C or higher (hereinafter, the solvent is also referred to as "solvent (E1)"), and the content of the solvent (E1) is the curable resin composition More than 20% by mass of the total mass of the solvent.

<Resin (A)>

The resin (A) is preferably a thermosetting resin, and a resin that hardens by heat above 60°C is more preferable, and a copolymer containing the following structural unit is more preferable: derived from unsaturated The structural unit of at least one monomer in the group consisting of carboxylic acid and unsaturated carboxylic anhydride (this monomer is also referred to as "(a)"), and is derived from a cyclic ether having a carbon number of 2 to 4 The structural unit of the monomer of the structure and ethylenically unsaturated bond (this monomer is also referred to as "(b)").

The polymer may further have a structural unit that can be copolymerized with (a) and is derived from a monomer that does not have a cyclic ether structure with a carbon number of 2 to 4 (the monomer is also referred to as "(c)").

The resin (A) is preferably the following resin [K1] and resin [K2].

Resin [K1]: Copolymer of (a) and (b); Resin [K2]: Copolymer of (a), (b) and (c).

Examples of (a) include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and vinyl p-benzoate; maleic acid, fumaric acid, citracan Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid , 1,2,3,6-tetrahydroo Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene , 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] Bicyclic unsaturated compounds containing carboxyl groups such as heptyl-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride Dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6 -Dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2- Unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids with more than two valences, such as (meth)acryloxyethyl] ester; α-(hydroxymeth)acrylic acid, etc. are in the same Unsaturated acrylates containing hydroxyl and carboxyl groups in the molecule.

Among these, in terms of copolymerization reactivity or solubility in alkaline solutions, (a) is preferably (meth)acrylic acid, maleic anhydride, etc., and (meth)acrylic acid is more preferable . In addition, in this specification, the "(meth)acryloyl group" means at least one selected from the group consisting of an acryloyl group and a methacryloyl group. Symbols such as "(meth)acrylic acid" and "(meth)acrylate" also have the same meaning.

(b) refers to, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) At least one of the group consisting of) and ethylenically unsaturated bond polymerizable compound. (b) A monomer having a cyclic ether structure with a carbon number of 2 to 4 and a (meth)acryloxy group is preferred.

(b) Examples include: monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond The monomer (b2) (hereinafter also referred to as "(b2)"), the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)").

(b1) Examples include monomers (b1-1) (hereinafter also referred to as "(b1-1)") having a linear or branched unsaturated aliphatic hydrocarbon epoxidized structure and Monomer (b1-2) (hereinafter also referred to as "(b1-2)") having an epoxidized structure of unsaturated alicyclic hydrocarbon.

(b1-1) Examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl ethylene Base ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether Ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2, 3,4-gins (glycidoxymethyl) styrene, 2,3,5-gins (glycidoxymethyl) styrene, 2,3,6-gins (glycidoxymethyl) benzene Ethylene, 3,4,5-ginseng (glycidoxymethyl) styrene, 2,4,6-ginseng (glycidoxymethyl) styrene, etc.

(b1-2) Examples include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel Chemical Industry Co., Ltd.), 3,4 -Epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer-A400; Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer-M100; Daicel Chemical Industry Co., Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), etc.

[In formula (I) and formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^b1 represents a single bond and X ^{b2 system, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -NH-. R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. ＊ means the bond with O. ]

The alkyl group having 1 to 4 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, and the like. Alkyl groups in which hydrogen atoms are substituted with hydroxy groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy- 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. R ^b1 and R ^b2 preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably include a hydrogen atom and a methyl group.

Alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl Base, hexane-1,6-diyl, etc. X ^b1 and X ^b2 preferably include single bond, methylene, ethylene, *-CH ₂ -O-, *-CH ₂ CH ₂ -O-, more preferably single bond, *-CH ₂ CH ₂ -O-. * Means the bond with O.

The compound represented by formula (I) includes a compound represented by any one of formula (I-1) to formula (I-15), and the like. Among them, the formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I- The compound represented by 15) is preferred, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

The compound represented by formula (II) includes a compound represented by any of formula (II-1) to formula (II-15), and the like. Among them, the formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II- The compound represented by 15) is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, respectively, or may be mixed and used in any ratio. When mixed and used, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) The rate, based on moles, is preferably from 5:95 to 95:5, more preferably from 10:90 to 90:10, and even more preferably from 20:80 to 80:20.

(b2) A monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. (b2) Examples include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl -3-Methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyl Oxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl 3-propenyloxyethyl oxetane and the like.

(b3) is preferably a monomer having a tetrahydrofuran group and a (meth)acryloxy group. (b3) Examples include tetrahydrofuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuryl methacrylate, and the like.

As far as the heat resistance, chemical resistance and other reliability of the cured film obtained can be made higher, (b) is preferably (b1). In addition, in terms of improving the storage stability of the curable resin composition, (b1-2) is more preferable.

(c) Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and third butyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2.6 ] decane-8-yl (meth)acrylate (in this technical field, customary The name is "dicyclopentyl (meth) acrylate." At the same time, it is also called "tricyclodecyl (meth)acrylate.), tricyclo[5.2.1.0 ^2.6 ] decene-8-yl (methyl) ) Acrylate (in this technical field, the traditional name is "dicyclopentenyl (meth) acrylate".), dicyclopentyloxyethyl (meth)acrylate, norbornene (meth) Isobornyl acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth) ) (Meth)acrylates such as benzyl acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; butene Diethyl diacid, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1] Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept- 2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[ 2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-di Ethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept -2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-ring Hexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2 .1]Hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- Succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6 -Maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide, etc. Dicarbonyl imine derivatives; styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylic acid Nitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butane Diene and so on.

In terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N- Benzyl maleimide and bicyclo[2.2.1]hept-2-ene are preferred.

In resin [K1], the ratio of the structural units derived from each monomer relative to the total structural units constituting the resin [K1] is based on the structural unit derived from (a): 5 to 60 mol%, source Structural unit derived from (b): 40 to 95 mol% preferably, and structural unit derived from (a): 10 to 50 mol%, structural unit derived from (b): 50 to 90 Mole% is better.

When the ratio of the structural units constituting the resin [K1] is within the above-mentioned range, the storage stability of the curable resin composition, the chemical resistance, heat resistance, and mechanical strength of the cured film obtained tend to be improved.

For resin [K1], please refer to the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House: Chemical Doujin (Stock) 1st Edition, 1st Brush, March 1, 1972) and the document. Manufactured by the references mentioned.

Specifically, it can be mentioned that a predetermined amount of (a) and (b), polymerization initiator, solvent, etc. are placed in a reaction vessel, for example, nitrogen is substituted for oxygen to create a deoxidizing atmosphere, and heating and heat preservation are performed while stirring. Methods. In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and ordinary users in the field can be used. The polymerization initiator includes, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (Benzoyl peroxide, etc.); The solvent may be any solvent as long as it can dissolve each monomer, and examples of the solvent include the solvents described below used in the curable resin composition.

In addition, the obtained resin may be used as it is as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may also be used. In particular, as a polymerization solvent, by using the solvent in the curable resin composition of the present invention, the reacted solution can be directly used in the production of the curable resin composition, so the production of the curable resin composition can be simplified. Process.

In resin [K2], in the total structural units constituting resin [K2], the ratio derived from each structural unit is based on the structural unit derived from (a): 2-40 mol%, derived from ( b) structural unit: 2 to 95 mol%, structural unit derived from (c): 1 to 65 mol%, and preferably Structural unit derived from (a): 5 to 35 mol%, structural unit derived from (b): 5 to 80 mol%, structural unit derived from (c): 1 to 60 mol% Better.

At the same time, relative to the total number of moles of all structural units constituting the resin [K2], the total amount of the structural units derived from (a) and the structural units derived from (b) is 70 to 99 mole% It is better, and more preferably 90 to 99 mol%. When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable resin composition, the chemical resistance, heat resistance, and mechanical strength of the cured film obtained tend to be improved. Resin [K2] can be manufactured by the same method as resin [K1].

Specific examples of resin [K1] include (meth)acrylic acid/compound represented by formula (I-1) (hereinafter, this compound is also simply referred to as "formula (I-1)". Formula (I-2) is represented by The compound represented by other formulas such as the compound is also represented by the same abbreviation (only the formula).) Copolymer, (meth)acrylic acid/copolymer of formula (I-2), (meth)acrylic acid/formula (I-3) copolymer, (meth)acrylic acid/copolymer of formula (I-4), (meth)acrylic acid/copolymer of formula (I-5), (meth)acrylic acid/ Copolymer of formula (I-6), (meth)acrylic acid/copolymer of formula (I-7), (meth)acrylic acid/copolymer of formula (I-8), (meth)acrylic acid /Copolymer of formula (I-9), (meth)acrylic acid/copolymer of formula (I-10), (meth)acrylic acid/copolymer of formula (I-11), (meth) Acrylic acid/copolymer of formula (I-12), (meth)acrylic acid/copolymer of formula (I-13), (meth)acrylic acid/copolymer of formula (I-14), (meth)acrylic acid/copolymer of formula (I-14), (meth)acrylic acid/copolymer of formula (I-14), )Acrylic acid/copolymer of formula (I-15), (meth)acrylic acid/copolymer of formula (II-1), (meth)acrylic acid/copolymer of formula (II-2), (former Base) acrylic/ Copolymer of formula (II-3), (meth)acrylic acid/copolymer of formula (II-4), (meth)acrylic acid/copolymer of formula (II-5), (meth)acrylic acid /Copolymer of formula (II-6), (meth)acrylic acid/copolymer of formula (II-7), (meth)acrylic acid/copolymer of formula (II-8), (meth) Acrylic acid/copolymer of formula (II-9), (meth)acrylic acid/copolymer of formula (II-10), (meth)acrylic acid/copolymer of formula (II-11), (meth)acrylic acid/copolymer of formula (II-11), (meth)acrylic acid/copolymer of formula (II-11), )Acrylic acid/copolymer of formula (II-12), (meth)acrylic acid/copolymer of formula (II-13), (meth)acrylic acid/copolymer of formula (II-14), (formula (II-14) copolymer Base) acrylic acid/copolymer of formula (II-15), (meth)acrylic acid/copolymer of formula (I-1)/formula (II-1), (meth)acrylic acid/copolymer of formula (I-2) )/Copolymer of formula (II-2), (meth)acrylic acid/copolymer of formula (I-3)/formula (II-3), (meth)acrylic acid/copolymer of formula (I-4)/ The copolymer of formula (II-4), the copolymer of (meth)acrylic acid/formula (I-5)/formula (II-5), (meth)acrylic acid/formula (I-6)/formula ( II-6) copolymer, (meth)acrylic acid/formula (I-7)/formula (II-7) copolymer, (meth)acrylic acid/formula (I-8)/formula (II- 8) Copolymer, (meth)acrylic acid/formula (I-9)/formula (II-9) copolymer, (meth)acrylic acid/formula (I-10)/formula (II-10) Copolymer of (meth)acrylic acid/formula (I-11)/formula (II-11), (meth)acrylic acid/formula (I-12)/formula (II-12) Polymer, copolymer of (meth)acrylic acid/formula (I-13)/formula (II-13), copolymer of (meth)acrylic acid/formula (I-14)/formula (II-14) , (Meth)acrylic acid/formula (I-15)/formula (II-15) copolymer, (meth)acrylic acid/formula (I-1)/formula (I-7) copolymer, ( Meth) acrylic acid/copolymer of formula (I-1)/formula (II-7), crotonic acid/copolymer of formula (I-1), crotonic acid/copolymer of formula (I-2) , Crotonic acid/copolymer of formula (I-3), crotonic acid/formula (I-4) Copolymer, crotonic acid/copolymer of formula (I-5), crotonic acid/copolymer of formula (I-6), crotonic acid/copolymer of formula (I-7), crotonic acid/ Copolymer of formula (I-8), crotonic acid/copolymer of formula (I-9), crotonic acid/copolymer of formula (I-10), crotonic acid/copolymer of formula (I-11) Polymer, crotonic acid/copolymer of formula (I-12), crotonic acid/copolymer of formula (I-13), crotonic acid/copolymer of formula (I-14), crotonic acid/copolymer of formula (I-14) I-15) copolymer, crotonic acid/copolymer of formula (II-1), crotonic acid/copolymer of formula (II-2), crotonic acid/copolymer of formula (II-3) , Crotonic acid/copolymer of formula (II-4), crotonic acid/copolymer of formula (II-5), crotonic acid/copolymer of formula (II-6), crotonic acid/copolymer of formula (II- 7) Copolymer, crotonic acid/copolymer of formula (II-8), crotonic acid/copolymer of formula (II-9), crotonic acid/copolymer of formula (II-10), croton Acid/copolymer of formula (II-11), crotonic acid/copolymer of formula (II-12), crotonic acid/copolymer of formula (II-13), crotonic acid/copolymer of formula (II-14) Copolymer, crotonic acid/copolymer of formula (II-15), maleic acid/copolymer of formula (I-1), maleic acid/copolymer of formula (I-2) Polymer, maleic acid/copolymer of formula (I-3), maleic acid/copolymer of formula (I-4), maleic acid/copolymer of formula (I-5) Copolymer, maleic acid/copolymer of formula (I-6), maleic acid/copolymer of formula (I-7), maleic acid/copolymer of formula (I-8) Copolymer, maleic acid/copolymer of formula (I-9), maleic acid/copolymer of formula (I-10), maleic acid/copolymer of formula (I-11) ) Copolymer, maleic acid/copolymer of formula (I-12), maleic acid/copolymer of formula (I-13), maleic acid/copolymer of formula (I- 14) Copolymer, maleic acid/copolymer of formula (I-15), maleic acid/copolymer of formula (II-1), maleic acid/copolymer of formula (II-1), maleic acid/copolymer of formula (II-1) Acid/copolymer of formula (II-2), maleic acid/copolymer of formula (II-3), maleic acid/copolymer of formula (II-4), maleic acid Diacid/copolymer of formula (II-5), maleic acid/copolymer of formula (II-6), maleic acid/copolymer of formula (II-7), maleic acid/copolymer of formula (II-7) Acrylic acid/copolymer of formula (II-8), maleic acid/copolymer of formula (II-9), maleic acid/copolymer of formula (II-10), cis Butenedioic acid/copolymer of formula (II-11), maleic acid/copolymer of formula (II-12), maleic acid/copolymer of formula (II-13), Maleic acid/copolymer of formula (II-14), maleic acid/copolymer of formula (II-15), (meth)acrylic acid/maleic anhydride/copolymer of formula (I- 1) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-2), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-3) Polymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-4), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-5), ( Meth)acrylic acid/maleic anhydride/copolymer of formula (I-6), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-7), (meth)acrylic acid /Maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-9), (meth)acrylic acid/maleic Diacid anhydride/copolymer of formula (I-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-11), (meth)acrylic acid/maleic anhydride/formula (I-12) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-13), (meth)acrylic acid/maleic anhydride/formula (I-14) ), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-15), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1) Compound, (meth)acrylic acid/maleic anhydride/formula (II-2) Polymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-3), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-4), ( Meth) acrylic acid/maleic anhydride/copolymer of formula (II-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-6), (meth)acrylic acid /Maleic anhydride/copolymer of formula (II-7), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-8), (meth)acrylic acid/maleic Diacid anhydride/copolymer of formula (II-9), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-10), (meth)acrylic acid/maleic anhydride/copolymer (II-11) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-12), (meth)acrylic acid/maleic anhydride/formula (II-13) ) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-14), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-15) Things and so on.

Specific examples of the resin [K2] include (meth)acrylic acid/formula (I-1)/(meth)acrylic acid methyl ester copolymer, (meth)acrylic acid/formula (I-2)/( Copolymer of methyl meth)acrylate, copolymer of (meth)acrylic acid/formula (I-3)/methyl (meth)acrylate, (meth)acrylic acid/formula (I-4)/( Copolymer of methyl meth)acrylate, copolymer of (meth)acrylic acid/formula (I-5)/methyl (meth)acrylate, (meth)acrylic acid/formula (I-6)/( Copolymer of methyl meth)acrylate, copolymer of (meth)acrylic acid/formula (I-7)/(meth)acrylate, (meth)acrylic acid/formula (I-8)/( Copolymer of methyl meth)acrylate, copolymer of (meth)acrylic acid/formula (I-9)/methyl (meth)acrylate, (meth)acrylic acid/formula (I-10)/( Copolymer of methyl meth)acrylate, (meth)acrylic acid / formula (I-11)/(meth)acrylic acid/methyl acrylate copolymer, (meth)acrylic acid/formula (I-12)/(meth)methyl acrylate copolymer, (meth)acrylic acid/formula (I-13)/(meth)acrylate copolymer, (meth)acrylic acid/formula (I-14)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (I-15)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-1)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-2)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-3)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-4)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-5)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-6)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-7)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-8)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-9)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-10)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-11)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-12)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-13)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (II-14)/(meth)acrylate copolymer, (meth)acrylic acid/formula (II-15)/(meth)methylacrylate copolymer, (meth)acrylic acid/formula (I-1)/Dicyclopentyl (meth)acrylate copolymer, (meth)acrylic acid/Formula (II-1)/Dicyclopentyl (meth)acrylate copolymer, ( Meth) acrylic acid/formula (I-1)/formula (II-1)/dicyclopentyl (meth)acrylate copolymer, crotonic acid/formula (I-1)/dicyclopentyl (formula) Base) acrylate co Polymer, maleic acid/formula (I-1)/dicyclopentyl (meth)acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1)/ Copolymer of dicyclopentyl (meth)acrylate, copolymer of (meth)acrylic acid/formula (I-1)/methyl (meth)acrylate/dicyclopentyl (meth)acrylate , Crotonic acid/formula (II-1)/dicyclopentyl (meth)acrylate copolymer, maleic acid/formula (II-1)/dicyclopentyl (meth)acrylate Copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/dicyclopentyl (meth)acrylate copolymer, (meth)acrylic acid/formula (II-1) /(Meth)acrylate/dicyclopentyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-1)/(meth)phenyl acrylate copolymer, ( Copolymer of meth)acrylic acid/formula (II-1)/(meth)acrylic acid phenyl ester, (meth)acrylic acid/formula (I-1)/formula (II-1)/(meth)acrylic acid benzene Ester copolymer, crotonic acid/formula (I-1)/(meth) phenyl acrylate copolymer, maleic acid/formula (I-1)/(meth) phenyl acrylate copolymer Polymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/(meth)acrylic acid phenyl ester, (meth)acrylic acid/formula (I-1)/(methyl) ) Copolymer of methyl acrylate/phenyl(meth)acrylate, crotonic acid/formula (II-1)/phenyl(meth)acrylate copolymer, maleic acid/formula (II-1) )/(Meth)phenyl acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/(meth)phenyl acrylate copolymer, (meth)acrylic acid /Formula (II-1)/(meth)acrylate/(meth)phenyl acrylate copolymer, (meth)acrylic acid/formula (I-1)/diethyl maleate Copolymer, (meth)acrylic acid/formula (II-1)/diethyl maleate copolymer, (meth)acrylic acid/formula (I-1)/formula (II-1)/ Diethyl maleate Copolymer of crotonic acid/formula (I-1)/diethyl maleate, copolymer of maleic acid/formula (I-1)/diethyl maleate Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/diethyl maleate, (meth)acrylic acid/formula (I-1)/( Copolymer of methyl methacrylate/diethyl maleate, copolymer of crotonic acid/formula (II-1)/diethyl maleate, maleic acid/formula (II-1)/Copolymer of diethyl maleate, (Meth)acrylic acid/Maleic anhydride/Copolymer of formula (II-1)/Diethyl maleate , (Meth)acrylic acid/formula (II-1)/(meth)acrylate/diethyl maleate copolymer, (meth)acrylic acid/formula (I-1)/(former Copolymer of 2-hydroxyester ethyl acrylate, copolymer of (meth)acrylic acid/formula (II-1)/2-hydroxyester ethyl (meth)acrylate, (meth)acrylic acid/formula (I-1)/Formula (II-1)/Copolymer of 2-hydroxyethyl (meth)acrylate, crotonic acid/Formula (I-1)/2-hydroxyethyl (meth)acrylate Copolymer of maleic acid/formula (I-1)/(meth)acrylic acid 2-hydroxy ester ethyl copolymer, (meth)acrylic acid/maleic anhydride/formula (I- 1)/Copolymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/formula (I-1)/methyl (meth)acrylate/2-hydroxyethyl (meth)acrylate Ester copolymer, crotonic acid/formula (II-1)/(meth)acrylate 2-hydroxyester ethyl copolymer, maleic acid/formula (II-1)/(meth)acrylic acid Copolymer of ethyl 2-hydroxyester, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/2-hydroxyester ethyl (meth)acrylate, (meth) Copolymer of acrylic acid/formula (II-1)/methyl (meth)acrylate/2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/formula (I-1)/bicyclo[2.2. 1) Copolymer of hept-2-ene, (meth)acrylic acid/formula (II-1)/ Copolymer of bicyclo[2.2.1]hept-2-ene, copolymerization of (meth)acrylic acid/formula (I-1)/formula (II-1)/bicyclo[2.2.1]hept-2-ene Compound, crotonic acid/formula (I-1)/bicyclo[2.2.1]hept-2-ene copolymer, maleic acid/formula (I-1)/bicyclo[2.2.1]hept-2 -Ene copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1)/bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid/formula ( I-1)/Methyl(meth)acrylate/Bicyclo[2.2.1]hept-2-ene copolymer, crotonic acid/Formula (II-1)/Bicyclo[2.2.1]hept-2-ene Copolymer, maleic acid/formula (II-1)/bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid/maleic anhydride/formula (II- 1)/Bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid/formula (II-1)/(meth)acrylate/bicyclo[2.2.1]hept-2-ene Olefin copolymer, (meth)acrylic acid/formula (I-1)/N-cyclohexyl maleimide copolymer, (meth)acrylic acid/formula (II-1)/N- Copolymer of cyclohexyl maleimide, copolymer of (meth)acrylic acid/formula (I-1)/formula (II-1)/N-cyclohexyl maleimide, Crotonic acid/formula (I-1)/N-cyclohexylmaleimide copolymer, maleic acid/formula (I-1)/N-cyclohexylmaleimide Copolymer of (meth)acrylic acid/maleic anhydride/formula (I-1)/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/formula (I- 1)/(meth)acrylate/N-cyclohexylmaleimide copolymer, crotonic acid/formula (II-1)/N-cyclohexylmaleimide copolymer Polymer, maleic acid/formula (II-1)/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1) /N-cyclohexylmaleimide copolymer, (meth)acrylic acid/formula (II-1)/(meth)acrylate/N-cyclohexylmaleimide common Polymer, (meth)acrylic acid/formula (I-1)/styrene copolymer, (meth)acrylic acid/formula (II-1)/styrene copolymer, (meth)acrylic acid/formula (I-1)/Formula (II-1)/styrene copolymer, crotonic acid/formula (I-1)/styrene copolymer, maleic acid/formula (I-1)/ Copolymer of styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/styrene, (meth)acrylic acid/formula (I-1)/(meth) Methyl acrylate/styrene copolymer, crotonic acid/formula (II-1)/styrene copolymer, maleic acid/formula (II-1)/styrene copolymer, (formaldehyde) (Base) acrylic acid/maleic anhydride/formula (II-1)/styrene copolymer, (meth)acrylic acid/formula (II-1)/(meth)acrylic acid/methyl acrylate/styrene copolymer (Meth)acrylic acid/formula (I-1)/N-cyclohexylmaleimide/styrene copolymer, (meth)acrylic acid/formula (II-1)/N-ring Copolymer of hexyl maleimide/styrene, (meth)acrylic acid/formula (I-1)/formula (II-1)/N-cyclohexyl maleimide/styrene Copolymer, crotonic acid/formula (I-1)/N-cyclohexylmaleimide/styrene copolymer, maleic acid/formula (I-1)/N-ring Copolymer of hexylmaleimide/styrene, (meth)acrylic acid/maleic anhydride/formula (I-1)/N-cyclohexylmaleimide/styrene Copolymer, (meth)acrylic acid/formula (I-1)/methyl (meth)acrylate/N-cyclohexylmaleimide/styrene copolymer, crotonic acid/formula (II -1)/N-cyclohexylmaleimide/styrene copolymer, maleic acid/formula (II-1)/N-cyclohexylmaleimide/styrene Copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/N-cyclohexylmaleimide/styrene copolymer, (meth)acrylic acid/ Copolymer of formula (II-1)/methyl (meth)acrylate/N-cyclohexyl maleimide/styrene, etc.

The weight average molecular weight of the converted polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight of the resin (a) is within the aforementioned range, the coatability of the curable resin composition tends to be improved. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the aforementioned range, the chemical resistance of the cured film obtained tends to be improved.

The acid value of the resin (A) is preferably greater than 30mg-KOH/g and less than 180mg-KOH/g, and more preferably greater than 40mg-KOH/g and less than 150mg-KOH/g, and more than 50mg-KOH/g 135mg-KOH/g or less is better. Here, the acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and it can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the aforementioned range, the adhesion between the obtained cured film and the substrate tends to be improved.

Relative to the solid content of the curable resin composition of the present invention, the content of resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and more preferably 40 to 70% by mass . When the content of the resin (A) is within the aforementioned range, the cured film obtained will tend to be excellent in heat resistance, and the adhesiveness and chemical resistance to the substrate will tend to be improved. Here, the solid content of the curable resin composition refers to the amount obtained by excluding the content of the solvent (E) from the total amount of the curable resin composition of the present invention.

The curable resin composition of the present invention may further contain at least one selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins (hereinafter, the resin is also referred to as "epoxy resin"). Resin (C)") is referred to as resin (A).

The curable resin composition of the present invention preferably further contains at least one component selected from the group consisting of a reactive monomer (B), an antioxidant (F), and a surfactant (H).

The curable resin composition of the present invention may further contain at least one selected from a polymerization initiator (D), a polymerization initiator (D1), a thiol compound (T), and at least one selected from a polycarboxylic acid anhydride and a polycarboxylic acid At least one component in the group consisting of a compound (hereinafter also referred to as "polycarboxylic acid (G)") and an imidazole compound (J) in the group formed.

<Reactive monomer (B)>

The reactive monomer (B) contains a group having at least one selected from the group consisting of an acryl group and a methacryl group (hereinafter, also referred to as "(meth)acryl group") Compound (hereinafter, this compound is also referred to as "(meth)acrylic compound (B1)"), compound (B2) represented by formula (1) described later, and the like.

The (meth)acrylic compound (B1) may be a (meth)acrylic compound having one (meth)acrylic group, or a (meth)acrylic compound having two or more (meth)acrylic groups Acrylic compound.

The (meth)acrylic compound having one (meth)acryloyl group includes the same compounds as those exemplified in (a), (b), and (c) above. Among them, (methyl) ) Acrylate is preferred.

(Meth)acrylation with 2 (meth)acrylic groups Compounds include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylenedi Alcohol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A bis(meth)acrylate, propoxylate Alkylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, etc.

The (meth)acrylic compound having three or more (meth)acryloyl groups includes trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, ginseng (2 -Hydroxyethyl) isocyanurate tri(meth)acrylate (Tris(2-hydroxyethyl)isocyanurate tri(math)acrylate), ethoxylated trimethylolpropane tri(meth)acrylate, Propoxylated trimethylolpropane tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentyl erythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate Base) acrylate, trineopentaerythritol tetra(meth)acrylate, trineopentaerythritol penta(meth)acrylate, trineopentaerythritol hexa(meth)acrylate, trineopentaerythritol seven (Meth) acrylate, trineopentaerythritol octa(meth)acrylate, the reactant of neopentaerythritol tri(meth)acrylate and acid anhydride, dineopentaerythritol penta(meth)acrylate and The reactant of acid anhydride, the reactant of trineopentaerythritol hepta(meth)acrylate and acid anhydride, caprolactone modified trimethylolpropane tri(meth)acrylate, caprolactone modified neopentylerythritol Tri(meth)acrylate, caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified neopentyl erythritol tetra(meth)acrylic acid Modification of esters and caprolactone Dineopentaerythritol penta(meth)acrylate, caprolactone modified dineopentaerythritol hexa(meth)acrylate, caprolactone modified trineopentaerythritol tetra(meth)acrylate, hexamethylene Lactone modified trineopentaerythritol penta(meth)acrylate, caprolactone modified trineopentaerythritol hexa(meth)acrylate, caprolactone modified trineopentaerythritol seven(meth) Acrylate, caprolactone modified trineopentaerythritol octa(meth)acrylate, caprolactone modified reaction product of neopentylerythritol tri(meth)acrylate and acid anhydride, caprolactone modified two new The reactant of pentaerythritol penta(meth)acrylate and acid anhydride, the reactant of caprolactone modified trineopentaerythritol hepta(meth)acrylate and acid anhydride, etc.

The (meth)acrylic compound (B1) is preferably a (meth)acrylic compound having 3 or more (meth)acrylic acid groups, and more preferably dineopreitol hexa(meth)acrylate.

When the curable resin composition of the present invention contains the (meth)acrylic compound (B1), the content is preferably 20 to 100 parts by mass, and preferably 25 to 70 parts by mass relative to 100 parts by mass of the resin (a). Better servings. When the content of the (meth)acrylic compound is within the aforementioned range, the chemical resistance and mechanical strength of the cured film obtained can be improved.

Compound (B2) can be represented by formula (1).

[式(1)中，R¹、R²及R³係相互獨立的表示式(a)表示之基或式(b)表示之基。]

[In the formula (1), R ¹ , R ^2, and R ³ independently represent the group represented by the formula (a) or the group represented by the formula (b). ]

[式(a)及式(b)中，R⁴及R⁵，係相互獨立的表示氫原子或碳數1至8的烷基。]

[In formulas (a) and (b), R ⁴ and R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

The alkyl group having 1 to 8 carbons includes methyl, ethyl, propyl, isopropyl, butyl, pentyl, octyl and the like. R ⁴ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ⁵ is preferably a hydrogen atom or a methyl group.

It is preferable that at least one of R ¹ , R ² and R ³ is a group represented by formula (a).

The compound (B2) includes compounds represented by formula (1-1) to formula (1-7), and the like. In addition, compounds represented by formula (1-1) to formula (1-4) are preferred.

When the curable resin composition of the present invention contains the compound (B2), the content thereof is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass relative to 100 parts by mass of the resin (A). When the content of the compound (B2) is within the aforementioned range, the heat resistance of the cured film obtained can be improved.

<Epoxy resin (C)>

The epoxy resin (C) is at least one selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized by reacting a phenol compound or a polyhydric alcohol with epichlorohydrin. The glycidyl ether type epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, and o-cresol novolac type epoxy resins. Epoxy resin, ginseng hydroxyphenyl methane type epoxy resin.

The glycidyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure, and can be synthesized by reacting the carbonyl group of a phthalic acid derivative or fatty acid with epichlorohydrin. Examples of the glycidyl ester type epoxy resin include glycidyl ester type epoxy resins derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, and terephthalic acid.

In the curable resin composition of the present invention, the epoxy resin (C) is based on bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and o-cresol novolak type. Glycidyl ether type epoxy resins such as epoxy resin and polyphenol type epoxy resin are preferred. Among them, bisphenol A type epoxy resin is particularly preferred.

The glycidyl ether type epoxy resin can be synthesized by condensing a corresponding phenol compound and epichlorohydrin in the presence of a strong base using a conventionally known method. This reaction can be carried out by a method that the industry has always known. At the same time, commercially available products can also be used.

Commercial products of bisphenol A type epoxy resin include jER157S70, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (manufactured by Mitsubishi Chemical Corporation) and the like.

Commercial products of bisphenol F type epoxy resin include Epikote 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Toto Kasei Co., Ltd.), and the like.

Commercial products of phenol novolac epoxy resins include Epikote 152, Epikote 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), and DEN-438 (Dow Chemical Corporation) and so on.

Commercial products of o-cresol novolak type epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.) Wait.

Commercial products of polyphenol-type epoxy resins include Epikote 1032H60, Epikote YX-4000 (manufactured by Mitsubishi Chemical Corporation), and the like.

The epoxy equivalent of the epoxy resin (C) is preferably 100 to 500 g/eq, and more preferably 150 to 400 g/eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. The epoxy equivalent can be measured by, for example, the method specified in JIS K7236.

The acid value of the epoxy resin (C) is usually less than 30 mg-KOH/g, and preferably 10 mg-KOH/g or less. At the same time, the weight average molecular weight of the epoxy resin (C) is preferably 300 to 10,000, more preferably 400 to 6,000, and more preferably 500 to 4,800.

The curable resin composition of the present invention contains epoxy resin In the case of (C), the content is preferably 1 to 60 parts by mass, and more preferably 5 to 50 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). When the content of the epoxy resin (C) is within the aforementioned range, the adhesion between the obtained cured film and the substrate tends to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate a living radical, acid, etc. and initiate polymerization by the action of light or heat, and a known polymerization initiator can be used.

化合物、醯基氧化膦化合物及聯咪唑化合物所組成之群組中的至少1種聚合起始劑為佳，並以含有O-醯基肟化合物的聚合起始劑更佳。為此等的聚合起始劑時，具有高感度，且可趨使可見光域中的穿透率變高。 The polymerization initiator (D) is selected from the group consisting of O- oxime compounds, alkyl phenone compounds, three

At least one polymerization initiator from the group consisting of a compound, an acetoxy phosphine oxide compound, and a biimidazole compound is preferable, and a polymerization initiator containing an O-amino oxime compound is more preferable. In the case of such a polymerization initiator, it has high sensitivity and tends to increase the transmittance in the visible light range.

The O-acyl oxime compound is a compound having a structure represented by formula (d1).

Hereinafter, * means a bonding key.

O- oxime compounds, for example: N-benzyloxy-1-(4-phenylhydrothiophenyl)butane-1-one-2-imine (N-benzyloxy-1- (4-phenylsulfanylphenyl)butane-1-one-2-imine), N-benzyloxy-1-(4-phenylhydrosulfanylphenyl)octane-1-one-2-imine, N -Benzoyloxy -1-(4-phenylhydrothiophenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl- 4-(3,3-Dimethyl-2,4-dioxolylmethyloxy)benzyl}-9H-carbazol-3-yl)ethane-1-imine, N -Acetyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N -Benzoyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2 -Imines. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used.

The alkylphenone compound is a compound having a structure represented by formula (d2) or a structure represented by formula (d3). In these structures, the benzene ring may have a substituent.

The compound having the structure represented by the formula (d2) includes, for example, 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methanone Group]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used. At the same time, a polymerization initiator having a group capable of causing chain transfer described in Japanese Patent Application Publication No. 2002-544205 can also be used. The compound having the structure represented by the formula (d3) includes, for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2 -hydroxyl Ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Polymer, α,α-diethoxy acetophenone, benzyl dimethyl acetal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

化合物，可列舉例如：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

。 three

The compound includes, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by BASF Co., Ltd. in Japan) can also be used.

Bisimidazole compounds, including 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62-174204 Report etc.), an imidazole compound in which a phenyl group at the 4,4',5,5'-position is substituted with a carbonyl alkoxy group (see Japanese Patent Application Laid-Open No. 7-10913 etc.).

In addition, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzyl benzoate Ester, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) two Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2 -Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These compounds are preferably used in combination with the polymerization initiation aid (D1) (especially an amine compound) described later.

An acid generator can also be used as the polymerization initiator (D). Acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexa Onium salts such as fluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, or nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

When the curable resin composition of the present invention contains the polymerization initiator (D), its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) , And more preferably 0.5 to 15 parts by mass, and more preferably 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the above-mentioned range, the exposure time can be shortened due to high sensitivity, and the yield can be improved, and the visible light transmittance of the obtained pattern can be improved. Becomes high.

<Polymerization initiation aid (D1)>

The polymerization initiation aid (D1) can be used together with the polymerization initiator (D), and is a reactive monomer (B) used to promote the initiation of polymerization by the polymerization initiator (D) (for example, ( Meth) acrylic compound (B1)) polymerized compound or sensitizer.

The polymerization initiation auxiliary (D1) includes thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

The thiazoline compound includes compounds represented by formula (III-1) to formula (III-3), and the compounds described in JP 2008-65319 A, and the like.

Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-di Methyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's Ketone), 4,4'-bis(diethylamino)benzophenone Ketones, 4,4'-bis(ethylmethylamino)benzophenone, etc., among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 ,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

The thioxanthone compound includes 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone Ketones, 1-chloro-4-propoxythioxanthone, etc.

Carboxylic acid compounds include phenylsulfanyl acetic acid, methyl phenylsulfanyl acetic acid, ethyl phenyl sulfanyl acetic acid, methyl ethyl phenyl sulfanyl acetic acid, dimethyl phenyl sulfanyl acetic acid Glycolic acid, methoxyphenyl thioglycine, dimethoxyphenyl thioglycolic acid, chlorophenyl thioglycolic acid, dichlorophenyl thioglycolic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

When the curable resin composition of the present invention contains the polymerization initiation aid (D1), its content is based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), which is 0.1 to 30 parts by mass Better, and more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation assistant (D1) is within the aforementioned range, it tends to be more sensitive when forming a pattern.

<Thiol Compound (T)>

The thiol compound (T) is a compound having a hydrogen sulfide group (-SH) in the molecule. Among them, a compound having two or more sulfhydryl groups is preferred, and a compound having two or more sulfhydryl groups that bond with the carbon atoms of the aliphatic hydrocarbon structure is more preferred. The thiol compound (T) is preferably contained together with the polymerization initiator (D).

The thiol compound (T) includes, for example, hexamethylene dithiol, decane dithiol, 1,4-bis(methylhydrothio)benzene, butanediol bis(3-hydrothiopropionate), Butanediol bis(3-hydrothioacetate), ethylene glycol bis(3-hydrothioacetate), trimethylolpropane ginseng (3-hydrothioacetate), butanediol Bis(3-hydrothiopropionate), trimethylolpropane ginseng (3-hydrothiopropionate), trimethylolpropane ginseng (3-hydrothioacetate), neopentaerythritol Four (3-hydrothiopropionate), neopentylerythritol four (3-hydrothioacetate), ginseng hydroxyethyl ginseng (3-hydrothiopropionate), neopenteritol four ( 3-hydrothiobutyrate), 1,4-bis(3-hydrothiobutoxy)butane.

When the curable resin composition of the present invention contains the thiol compound (T), the content is preferably 10 to 90 parts by mass, and 15 to 70 parts by mass relative to 100 parts by mass of the polymerization initiator (D). Better servings. When the content of the thiol compound (T) is within the aforementioned range, the sensitivity tends to increase, and at the same time the developability becomes better.

<Antioxidant (F)>

The antioxidant (F) includes phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, in terms of reducing the coloration of the cured film, phenolic antioxidants are preferred.

-2,4,6(1H,3H,5H)-三酮、3,3’,3”,5,5’,5”-六-第三丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三-對-甲酚、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,6-二-第三丁基-4-甲基酚及6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜磷雜庚環(dioxaphosphepine)。前述酚系抗氧化劑，也可使用市售商品。市售的酚系抗氧化劑，可列舉例如：Sumilizer(註冊商標)BHT、GM、GS、GP(以上，全是住友化學(股)製)、Irganox(註冊商標)1010、1076、1330、3114(以上，全是BASF公司製)。 Phenolic antioxidants include, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2- [1-(2-hydroxy-3,5-di-tertiary amylphenyl) ethyl]-4,6-di-tertiary amyl phenyl acrylate, 3,9-bis[2-{3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[ 5.5) Undecane, 2,2'-methylene bis(6-tertiary butyl-4-methylphenol), 4,4'-butylene bis(6-tertiary butyl-3-methyl Phenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), 1 ,3,5-Ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, 3,3',3”,5,5',5”-hexa-tertiary butyl-a,a',a”-(both Trimethylbenzene-2,4,6-triyl) tri-p-cresol, neopentyl erythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-Di-tert-butyl-4-methylphenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4, 8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine. The aforementioned phenol-based antioxidant may also be commercially available. Examples of phenolic antioxidants sold include: Sumilizer (registered trademark) BHT, GM, GS, GP (all above, all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (above) , All made by BASF).

The sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-sulfur Substituted dipropionate, neopentyl erythritol base (3-lauryl thiopropionate). As the aforementioned sulfur-based antioxidant, commercially available products can also be used. Commercially available sulfur-based antioxidants include, for example, Sumilizer (registered trademark) TPL-R and TP-D (all above, all manufactured by Sumitomo Chemical Co., Ltd.).

Phosphorus antioxidants, for example: trioctyl phosphorous Ester, trilauryl phosphite, tridecyl phosphite, ginseng (nonylphenyl) phosphite, distearyl neopentyl phosphite, tetrakis (tridecyl)- 1,1,3-Sin (2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite. As the aforementioned phosphorus antioxidant, commercially available products can also be used. Examples of commercially available phosphorus-based antioxidants include Irgafos 168, 12, and 38 (all above, all manufactured by BASF Corporation), Adk Stab 329K, and Adk Stab PEP36 (all above, all manufactured by ADEKA Co., Ltd.).

Amine-based antioxidants include, for example, N,N'-di-second-butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, N,N'-di Cyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine. As the aforementioned amine-based antioxidant, commercially available products can also be used. Examples of commercially available amine antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all of the above are manufactured by Sumitomo Chemical Co., Ltd.).

When the curable resin composition of the present invention contains the antioxidant (F), the amount is based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), which is 0.1 parts by mass or more and 5 parts by mass or less Preferably, it is more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the aforementioned range, the heat resistance and pencil hardness of the cured film obtained tend to be improved.

<Surfactant (H)>

Surfactants (H) include, for example, polysiloxane-based surfactants that do not have fluorine atoms (hereinafter, the surfactant is also referred to as "polysiloxane-based surfactant"), fluorine-based surfactants, and Silicone-based surfactants based on fluorine atoms.

Polysiloxane-based surfactants include surfactants having siloxane bonds. Specifically, Toray Silicone DC3PA, the same series of SH7PA, the same series of DC11PA, the same series of SH21PA, the same series of SH28PA, the same series of SH29PA, the same series of SH30PA, polyether modified silicone oil SH8400 (product Name: Toray Dow Corning (stock)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 TSF4460 (manufactured by Momentive Performance Materials Japan) and the like.

The fluorine-based surfactant includes a surfactant having a fluorocarbon chain. Specifically, Fluorinert (registered trademark) FC 430, FC 431 of the same series (produced by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, F171 of the same series, F172 of the same series, F173 of the same series, F177 of the same series, F183 of the same series, F552 of the same series, F553 of the same series, F554 of the same series, F555 of the same series, F556 of the same series, 558 of the same series, F559 of the same series, R30 of the same series ( DIC (stock) system), EFTOP (registered trademark) EF301, the same series of EF303, the same series of EF351, the same series of EF352 (Mitsubishi Materials Electronic Chemicals (stock) system), Surflon (registered trademark) S381, the same series of S382 , The same series of SC101, the same series of SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute (stock)), etc.

Polysiloxane-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains. Specifically, you can cite Megafac (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, F443 of the same series (DIC (share) system), etc. And Megafac (registered trademark) F475 is better.

When the curable resin composition of the present invention contains a surfactant (H), its content relative to the total amount of the curable resin composition of the present invention is 0.001% by mass to 0.2% by mass, and 0.002% by mass to 0.1 Mass% or less is preferable, and 0.01 mass% or more and 0.05 mass% or less is more preferable. When the content of the surfactant (H) is within the aforementioned range, the flatness of the cured film can be improved.

<Polycarboxylic acid (G)>

The polycarboxylic acid (G) is at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids. Polycarboxylic acid refers to a compound having two or more carboxyl groups, and polycarboxylic acid anhydride refers to an anhydrate of polycarboxylic acid. The polycarboxylic acid (G) preferably has a molecular weight of 3,000 or less, and more preferably 1,000 or less.

The aforementioned polyvalent carboxylic acid anhydrides include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecyl succinic anhydride, 2-(2oct-3-enyl) Succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl) succinic anhydride, Tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Polycarboxylic acid anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methyl bicyclo[2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1] Heptane-2,3-dicarboxylic acid anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Acid anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and other alicyclic polycarboxylic acid anhydrides; phthalic anhydride, 3-vinyl Phthalic anhydride, 4-vinyl phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Tetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate), glycerol ginseng (dehydrated trimellitate), glycerol ginseng (dehydrated trimellitate) monoacetate, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxa-3-furyl)naphthalene[1,2-c]furan-1,3-dione and other aromatic polyvalents Carboxylic anhydride. You can also use Adeka hardener-EH-700 (trade name (the same below), ADEKA (stock) system), Rikacid-HH, the same series-TH, the same series-MH, the same series MH-700 (new Japan Physicochemical (stock) system), Epikinia 126, YH-306 of the same series, DX-126 of the same series (Shell Epoxy (stock)) and other commercial products.

The aforementioned polycarboxylic acids include: oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, chain polycarboxylic acid introduced with chain polycarboxylic acid anhydride, etc. Acid; cyclohexanedicarboxylic acid, alicyclic polycarboxylic acid introduced with alicyclic polycarboxylic acid anhydride, etc.; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid Aromatic polycarboxylic acids such as acids, polycarboxylic acids introduced into aromatic polycarboxylic acid anhydrides; etc.

Among them, in terms of improving the heat resistance of the cured film, especially not easily reducing the transparency in the visible light range, chain carboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferred, and alicyclic polycarboxylic acid anhydrides are more preferred. good.

When the curable resin composition of the present invention contains a polybasic acid (G), its content is relative to the total content of the resin (A) and the reactive monomer (B) 100 The part by mass is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and more preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G) is within the aforementioned range, the heat resistance and adhesion of the cured film can be improved.

<Imidazole Compound (J)>

The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy hardeners. Among them, the compound represented by formula (2) is preferred.

[式(2)中，R¹¹係表示碳數1至20的烷基、苯基、苯甲基或碳數2至5的氰基烷基。

[In formula (2), R ¹¹ represents an alkyl group having 1 to 20 carbons, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbons.

R ¹² to R ¹⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbons, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbons, the alkyl group and the phenyl group containing The hydrogen atom can be substituted by a hydroxyl group. ]

Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tertiary butyl, hexyl, heptyl, octyl, nonyl, decyl, and seventeen Alkyl, undecyl.

The cyanoalkyl group having 2 to 5 carbon atoms includes, for example, cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, and cyanopentyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, isobutyryl, pentamyl, isopentyl, trimethyl Acetyl (pivaloyl), lauryl, myristyl, and stearyl.

The imidazole compound (J) includes, for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methyl Imidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl -2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1 -Benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl 4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

When the curable resin composition of the present invention contains the imidazole compound (J), its content is based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), which is 0.1 parts by mass or more and 25 parts by mass or less Preferably, it is more preferably not less than 0.2 part by mass and not more than 15 parts by mass, and more preferably not less than 0.5 part by mass and not more than 5 parts by mass. When the content of the imidazole compound (J) is in the aforementioned range, the transparency of the obtained cured film in the visible light range tends to be improved.

<Solvent>

The curable resin composition of the present invention contains a solvent having a boiling point of 200°C or higher as the solvent. In this specification, "a solvent with a boiling point of 200°C or higher" is also referred to as "solvent (E1)".

The curable resin composition of the present invention may contain a solvent other than the solvent (E1) (hereinafter, this solvent is also referred to as "solvent (E2)") as the solvent.

The solvent (E1) is preferably 220°C or higher. At the same time, the boiling point of the solvent (E1) is preferably below 300°C.

The boiling point of solvent (E2) does not reach 200°C. The boiling point of the solvent (E2) is preferably above 100°C.

When the content of the solvent (E1) is in the aforementioned range, a cured film with high surface flatness can be formed.

The cured film is usually formed by applying a curable resin composition on a substrate and then drying it to form a composition layer and a heating step of heating the composition layer to form a cured film. With the curable resin composition of the present invention, a cured film with high surface flatness can be formed. It is presumed that the surface of the composition layer is easily flattened due to the effect of the solvent remaining in the composition layer during the heating step. It is caused by the heating step while keeping it in a flat state.

In addition, by setting the content of the solvent (E1) in the aforementioned range, it is estimated that the amount of solvent suitable for planarization may remain in the composition layer during the heating step.

The content of the solvent (E1) is preferably 80% by mass or less of the total mass of the solvent in the curable resin composition, and more preferably 60% by mass or less. By being in such a range, the solvent can be prevented from remaining in the cured film in the post-bake step.

The content of solvent (E2) is usually based on the curable resin group It is preferable that the total mass of the solvent in the finished product is 20% by mass or more, but less than 80% by mass.

Solvent (E2) should contain at least a solvent with a boiling point of 100°C or higher and less than 170°C (hereinafter, this solvent is also referred to as "solvent (E2-1)"), and a solvent with a boiling point of 170°C or higher and less than 200°C At least one of the solvent (hereinafter, the solvent is also referred to as "(E2-2)") is preferred, and it is more preferred to contain a solvent (E2-1), and to contain a solvent (E2-1) and a solvent (E2-2) ) Is better.

The content of the solvent (E2-1) is preferably 10% by mass or more of the total mass of the solvent in the curable resin composition, and more preferably 20% by mass or more.

When the curable resin composition of the present invention contains both the solvent (E2-1) and the solvent (E2-2), the ratio of the content of the solvent (E2-1) and the solvent (E2-2) (quality basis) is Solvent (E2-1): Solvent (E2-2)=10:90 to 50:50 is preferred.

When the curable resin composition of the present invention contains the solvent (E1) and the solvent (E2), the difference between the average boiling point of the solvent (E1) and the average boiling point of the solvent (E2) is preferably 80°C or higher.

The average boiling point of the solvent (E2) is preferably 170°C or less. The average boiling point of the solvent can be calculated from the boiling point of each solvent and its mass %. For example, a solvent composed of 80% by mass of a solvent with a boiling point of 160°C and 20% by mass of a solvent with a boiling point of 180°C has an average boiling point of 164°C (=160°C×0.8+180°C×0.2), and the boiling point is 160°C The average boiling point of the solvent composed of 100% by mass of the solvent is 160°C.

Solvent (E1) is nothing special as long as the boiling point is above 200℃ Limitations of the butyl ether include: triethylene glycol monobutyl ether (boiling point 283°C), dipropylene glycol monopropyl ether (boiling point 213°C), diethylene glycol monoethyl ether (boiling point 202°C), dipropylene glycol n-butyl ether (boiling point 229℃), tripropylene glycol methyl ether (boiling point 242℃), tripropylene glycol n-butyl ether (boiling point 274℃) and other ether solvents; 1,2,3-triethoxypropane (boiling point 260℃), 1,3-butane Ester solvents such as glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C), and 1,4-butanediol diacetate (boiling point 232°C); two Ethylene glycol monobutyl ether acetate (boiling point 246.7°C), diethylene glycol monoethyl ether acetate (boiling point 217°C) and other ether ester solvents; 1,3-butanediol (boiling point 208°C) and other alcohol solvents; Wait.

Solvent (E1) is selected from 1,3-butanediol diacetate, 1,6-hexanediol diacetate, 1,2,3-triethoxypropane and triethylene glycol mono At least one of the group consisting of butyl ether is preferred.

The solvent (E2) is not particularly limited as long as the boiling point is less than 200°C. Examples include: diethylene glycol dimethyl ether (boiling point 162°C), diethylene glycol diethyl ether (boiling point 189°C), and diethylene glycol Ethyl methyl ether (boiling point 176°C), dipropylene glycol dimethyl ether (boiling point 171°C), ethylene glycol monomethyl ether (boiling point 125°C), ethylene glycol monoethyl ether (boiling point 135°C), propylene glycol monomethyl ether ( (Boiling point 120℃), propylene glycol monoethyl ether (boiling point 133℃), propylene glycol monopropyl ether (boiling point 149℃), diethylene glycol methyl ethyl ether (boiling point 176℃) and other ether solvents; methyl pyruvate (boiling point 138℃) ), butyl propionate (boiling point 145℃), methyl lactate (boiling point 155℃), ethyl lactate (boiling point 155℃), ethyl pyruvate (boiling point 144℃) and other ester solvents; 2-heptanone (boiling point 151 ℃), 4-hydroxy-4-methyl-2-pentanone (boiling point 166 ℃), diisobutyl ketone (boiling point 168.4℃), cyclohexanone (boiling point 155℃) and other ketone solvents; xylene (boiling point 144℃) and other aromatic hydrocarbon solvents; 1-butanol (boiling point 117.6℃), 2- Alcohol solvents such as butanol (boiling point 98℃), isobutanol (boiling point 108℃); 3-methoxybutyl acetate (boiling point 172℃), propylene glycol monomethyl ether acetate (boiling point 146℃), propylene glycol Monoethyl ether acetate (boiling point 146℃), propylene glycol monomethyl ether propionate (boiling point 161℃), ethylene glycol monomethyl ether acetate (boiling point 144.5℃), ethylene glycol monoethyl ether acetate (boiling point 156 ℃), ether ester solvents such as methyl 3-methoxypropionate (boiling point 142 to 143℃); amine solvents such as N,N-dimethylformamide (boiling point 153℃); etc.

Solvent (E2-1) is preferably methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate and ethylene glycol monomethyl ether acetate, and Methoxybutanol and propylene glycol monoethyl ether acetate are more preferred.

Solvent (E2-2) is based on diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether and 3-methoxybutyl Acetate is preferred, and diethylene glycol methyl ethyl ether is more preferred.

Relative to the total amount of the curable resin composition of the present invention, the content of the solvent (E) is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. When the content of the solvent (E) is in the aforementioned range, the flatness of the film obtained by coating the curable resin composition tends to be high.

<Other ingredients>

The curable resin composition of the present invention may contain fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and other additives known in the art as necessary. .

The filler includes glass, silica, alumina, and the like. Other polymer compounds include thermosetting resins such as maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. Thermoplastic resin, etc. Examples of thermal radical generators include 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. Examples of ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. The chain transfer agent includes dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.

Adhesion promoters include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy silane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-Hydroxythiopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane , N-2-(aminoethyl)-3-aminopropylmethyl diethoxysilane, N-2-(aminoethyl) Ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl diethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc.

The curable resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the curable resin composition of the present invention, the content of the colorant relative to the entire composition is usually less than 1% by mass, and preferably less than 0.5% by mass.

The curable resin composition of the present invention is filled in a quartz cell with an optical path length of 1 cm, and when the transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is 70% or more. Better, and more than 80% is even better.

When the curable resin composition of the present invention is formed into a cured film, the average penetration rate of the cured film is preferably 90% or more, and more preferably 95% or more. The average transmittance is the average value of a cured film with a thickness of 2 μm after heat curing (100 to 250° C., 5 minutes to 3 hours), measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer. Therefore, it is possible to provide a cured film excellent in transparency in the visible light range.

<Manufacturing method of curable resin composition>

The curable resin composition of the present invention can be obtained by combining the resin (A) and the solvent (E1), and optionally the reactive monomer (B), the epoxy resin (C), and the polymerization initiator ( D), polymerization initiation aid (D1), antioxidant (F), surfactant (H), polycarboxylic acid (G), imidazole compound (J), solvent (E2), and other ingredients by known methods Made by mixing. After mixing, tie through holes A filter with a diameter of about 0.05 to 1.0 μm is preferred.

<Method of manufacturing cured film>

The method for producing a cured film of the present invention includes the step of applying the above-mentioned curable resin composition of the present invention on a substrate; and the step of heating the applied curable resin composition. Generally, the method for producing a cured film of the present invention includes the following steps (1) to (3).

Step (1): Step of applying the curable resin composition of the present invention to a substrate

Step (2): A step of drying the coated curable resin composition under reduced pressure to form a composition layer

Step (3): the step of heating the composition layer

Meanwhile, when the curable resin composition of the present invention contains a polymerization initiator (D), a cured film having a pattern can be produced by performing the following steps.

Step (1): Step of applying the curable resin composition of the present invention to a substrate

Step (2): A step of drying the coated curable resin composition under reduced pressure to form a composition layer

Step (2a): the step of exposing the composition layer through the photomask

Step (2b): the step of developing the exposed composition layer

Step (3a): the step of heating the developed composition layer

Step (1) is a step of applying the curable resin composition of the present invention to a substrate. The substrate may include glass, metal, plastic, etc., and color filters, insulating films, conductive films, and/or driving circuits may also be formed on the substrate. The coating on the substrate is preferably carried out by using a coating device such as a spin coater, a slit and spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Step (2) is a step of drying the applied curable resin composition under reduced pressure to form a composition layer. By performing this step, volatile components such as solvents in the curable resin composition can be removed.

Drying under reduced pressure is preferably carried out in a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa. Before or after drying under reduced pressure, heat drying (pre-baking) may also be performed. Heating and drying are usually carried out using heating devices such as ovens and hot plates. The temperature for heating and drying is preferably 30 to 120°C, and more preferably 50 to 110°C. Meanwhile, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

Step (3) is a step of heating the composition layer (post-baking). The composition layer is cured by heating to form a cured film. Heating is usually carried out using heating devices such as ovens and hot plates. The heating temperature is preferably 130 to 270°C, preferably 150 to 260°C, and more preferably 200 to 250°C. When the heating temperature is 200 to 250°C, it can prevent unnecessary solvents from remaining on the cured film. The heating time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

In the present invention, when the mass of the curable resin composition during coating in step (1) is set to 100, the mass of the composition layer supplied to the heating step is preferably 30 or more, and more preferably 40 or more , And more than 60 is better.

In terms of improving the flatness of the hardened film, The mass after coating the curable resin composition is set to 100, and the mass after pre-bake in step (2) is preferably 18 or more, and more preferably 23 or more, and the mass after step (3) is 23 or less Better, and more preferably less than 20. In addition, the mass immediately after application of the curable resin composition referred to here refers to the mass in a state where no solvent volatilization occurs, and is almost the same value as the mass of the curable resin composition used in the coating.

The curable resin composition of the present invention is coated on a substrate so that the film thickness after heat treatment becomes 1.8 μm, and is dried in sequence with a reduced pressure dryer at a temperature of 25° C. to a reduced pressure. During the reduced pressure drying treatment up to 66 Pa, the heat drying treatment heated at a temperature of 100°C for 3 minutes, and the heat drying treatment heated at a temperature of 230°C for 3 minutes, the mass of the curable resin composition immediately after coating is set to 100 When the mass of the curable resin composition film after the reduced pressure drying treatment and before the heat drying treatment is 30 or more, preferably 40 or more, and more preferably 60 or more, the curable resin composition after the heat treatment The quality of the film is preferably 20 or less. When the film obtained in each step satisfies the above numerical range, a cured film with high surface flatness can be formed.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. The mask can be used to form a light-shielding part corresponding to the part to be removed from the composition layer. There is no special restriction on the shape of the shading part, and it can be selected according to the purpose. The light source used in the exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter that blocks light below 350nm can be used to block this wavelength range, or a bandpass that can capture light near 436nm, 408nm, and 365nm can be used. Filter, and selectively capture these wavelength domains. Examples of light sources include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

In order to irradiate the parallel light uniformly on the entire exposure surface, or to perform precise alignment between the mask and the composition layer, it is better to use a mask aligner, stepper or other exposure device.

Step (2b) is a step of developing the exposed composition layer. By contacting the exposed composition layer with a developer solution for development, the unexposed part of the composition layer is dissolved in the developer solution and removed, and a patterned composition layer can be formed on the substrate. The developing solution is preferably an aqueous solution of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer solution may also contain a surfactant. The imaging method may be any method such as a pudding method, a dipping method, and a spray method. In addition, the substrate can be tilted at any angle during development. It is better to wash with water after development.

Step (3a) is a step of heating the developed composition layer. By performing the same heating as the aforementioned step (3), the patterned composition layer is cured, and a patterned cured film can be formed on the substrate.

The cured film obtained in this way has excellent surface flatness and can be used as, for example, a color filter substrate used in a liquid crystal display, an organic EL display, or an electronic paper, a protective film or a protective coating of a touch panel. Therefore, a display equipped with a high-quality cured film can be manufactured. In a color filter substrate having uneven surfaces with a colored pattern, a protective coating can be formed by the curable resin composition of the present invention, thereby improving the flatness of the surface. The thickness of the protective coating (when the coated surface has unevenness, the thickness from the surface of the protrusion) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less, and the coated surface has unevenness At this time, it is better to set at least 30% of the difference in height of the unevenness of the coated surface.

With the present invention, even with such a thin protective coating, the flatness of the surface can be improved. Since the protective coating is formed by the curable resin composition of the present invention, the unevenness of the surface of the protective coating can be made smaller than the unevenness of the coated surface.

[Example]

Hereinafter, the present invention will be explained in more detail through examples. The "%" and "parts" in the examples refer to mass% and parts by mass unless otherwise specified.

[Examples 1 to 7 and Comparative Example 1]

<Preparation of curable resin composition>

The ingredients shown in Table 1 were mixed in the proportions shown in Table 1, and in order to improve swelling, a fluorine-based surfactant (Megafac F554; manufactured by DIC) was added in an amount of 130 ppm relative to the total amount of the obtained mixture. ) As an additive to obtain a curable resin composition.

In addition, in Table 1, the number of parts contained in resin (a) means the mass parts of the converted solids, and the number of parts contained in components other than the solvent (hereinafter, this component is also referred to as "solids"), all means Let the total mass of the resin (A) and the reactive monomer (B) be the number of parts by mass in terms of 100 parts.

The details of each component are as follows.

Resin (A): Resin (Aa) synthesized by the following synthesis example 1

Epoxy resin (C): Bisphenol A epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Corporation),

Reactive monomer (B): Monoallyl diglycidyl isocyanurate (MA-DGIC; manufactured by Shikoku Chemical Industry Co., Ltd.) as compound (B2)

-2,4,6(1H,3H,5H)-三酮(IRGANOX(註冊商標)3114；BASF公司製)為硬化性樹脂(A)與反應性單體(B)的1質量份、 Antioxidant (F): 1,3,5-ginseng (4-hydroxy-3,5-di-tertiary butylbenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-trione (IRGANOX (registered trademark) 3114; manufactured by BASF Corporation) is 1 part by mass of the curable resin (A) and the reactive monomer (B),

Polycarboxylic acid (G): butane tetracarboxylic acid (Rikacid BT-W; New Japan Physical and Chemical Co., Ltd.),

Adhesion promoter: N-phenyl-3-aminopropyl trimethoxysilane (Silane coupling agent KBM573; Shin-Etsu Chemical Co., Ltd.),

Solvent (E1-1): 1,3-butanediol diacetate (BDGA) (boiling point 232°C),

Solvent (E1-2): Diethylene glycol monobutyl ether acetate (BDGAC) (boiling point 246.7°C),

Solvent (E1-3): 1,6-hexanediol diacetate (1,6-HDDA) (boiling point 260°C),

Solvent (E1-4): 1,2,3-triacetoxypropane (glyceryl triacetate) (boiling Point 260℃),

Solvent (E1-5): Triethylene glycol monobutyl ether (BTG) (boiling point 283℃),

Solvent (E2-1): Diethylene glycol methyl ethyl ether (EDM) (boiling point 176°C),

Solvent (E2-2): Methoxybutanol (MB) (boiling point 161°C),

Solvent (E2-3): propylene glycol monomethyl ether acetate (PGMA) (boiling point 146°C).

Solvent (E) is mixed so that the solid content of the curable resin composition becomes 15% by mass, and the values of solvents (E1-1) to (E1-5) and solvents (E2-1) to (E2-2) , Is the mass ratio (%) of the total weight of the solvent.

(Synthesis example 1)

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 L/min to make a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether were put in, and heated to 70° C. while stirring. Next, make 40 parts of methacrylic acid, and a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1) =50:50} After 360 parts are dissolved in 190 parts of diethylene glycol ethyl methyl ether, a solution is prepared, and the solution is dropped into a flask that has been kept warm at 70° C. using a drip pump over 4 hours.

On the other hand, a solution of 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethyl methyl ether, and the other The drip pump was dripped into the flask in 5 hours. After dropping the polymerization initiator solution, it was kept at 70°C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (Aa)) with a solid content of 42.3%. get The weight average molecular weight (Mw) of the resin Aa is 8,000, the molecular weight distribution (Mw/Mn) is 1.91, and the acid value in terms of solid content is 60 mg-KOH/g. It has the following structural units.

<Creation of Evaluation Board>

A 2-inch square glass substrate (EagleXG; manufactured by Corning) was washed with a neutral detergent, water, and isopropanol in this order, and then dried. The colored photosensitive resin composition (solid content 19%. Pigment, epoxy resin, acrylic monomer, polymerization initiator, adhesion improver, and surfactant are contained in the following proportions as solid content.) to post-baking The latter was spin-coated on this substrate so that the film thickness became 2.0 μm.

‧The content of each component in the colored photosensitive resin composition (the ratio of solid matter)

Pigment: about 40% (Note: the proportion of green pigment in the total amount of pigment: about 90%, the proportion of yellow colorant in the total amount of pigment: 10%), epoxy resin: 3%, acrylic monomer: 14% , Polymerization initiator: 10%, adhesion improver: 1%, surfactant: 600ppm

Next, in a clean oven, pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, set the distance between the coloring composition layer on the substrate and the quartz glass mask to 100 μm, and use an exposure machine (TME-150RSK; Topcon (stock) system, light source; ultra-high pressure mercury lamp) in an atmospheric environment. Light irradiation was performed at an exposure amount of 100 mJ/cm ^{2 (365nm standard).} In addition, this light irradiation is performed by passing the radiated light from the ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). At the same time, the photomask is used to form a line and space pattern with a line width of 30μm. The colored composition layer irradiated with light is immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of sodium hydroxide at 23°C for 60 seconds to develop the image. After washing with water, it is developed in an oven at 230°C Post-baking was performed for 30 minutes to prepare an evaluation substrate with a colored pattern of lines and spaces with a line width of 30 μm.

Using a contact film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.), the film thickness of the formed colored pattern was measured with a measuring width of 500 μm and a measuring speed of 10 seconds to obtain a curve of the surface shape of the colored pattern. At the same time, the average value of the film thickness of the colored pattern is calculated from the curve. The average film thickness is 2.0 μm.

<Creation of Cured Film>

Under the condition that the film thickness after post-baking (the film thickness from the surface of the colored pattern) becomes 1.0 μm, the curable resin compositions of Examples 1 to 7 and Comparative Example 1 were applied on the aforementioned evaluation substrate by spin coating .

Then, use a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) to depressurize and dry the rotary pump at 1000 rpm, booster pump at 700 rpm, and room temperature at 25°C until the reduced pressure reaches 66 Pa. The hot plate is pre-baked at a temperature of 100°C for 3 minutes. After cooling, the cured film was formed by post-baking at 230°C for 30 minutes.

Using a contact film thickness measuring device (DEKTAK6M; The thickness of the cured film on the evaluation substrate was measured with a measurement width of 500 μm and a measurement speed of 10 seconds, manufactured by ULVAC Co., Ltd., to obtain a curve of the surface shape of the cured film. When the average value of the film thickness of the cured film is calculated from this curve, the average value of the film thickness from the surface of the colored pattern is 1.0 μm.

<Flatness Evaluation>

Fig. 1 and Fig. 2 respectively show the curves of the outer shape of the colored patterns of Example 1 and Comparative Example 1 and the surface shape of the cured film. The horizontal axis indicates the position in the plane direction, and the vertical axis indicates the position in the height direction. A convex part of the curve of the surface shape of the outer shape of the colored pattern corresponds to a colored unit. At the same time, the average height difference of the uneven pattern on the surface of the cured film is calculated from the curve of the surface shape of the outer shape of the cured film. The results are shown in Table 1.

<Weight change>

A 2-inch square glass substrate (EagleXG; manufactured by Corning) was washed with a neutral detergent, water, and isopropanol in this order, and then dried. The curable resin compositions of Examples 1 to 7 and Comparative Example 1 were spin-coated on this substrate so that the film thickness after post-baking became 1.8 μm. Then, a cured film was formed in the same manner as the above-mentioned cured film was formed. In the preparation of the cured film, the quality of the substrate immediately after the application of the curable resin composition (including the quality of the coating film), the quality of the substrate after drying under reduced pressure (including the quality of the coating film), and the ratio of the pre-baked substrate were measured. Quality (including the quality of the coating film), the quality of the substrate after post-baking (including the quality of the cured film). The values obtained by subtracting the mass of the glass substrate from the respective measured values are shown in the "mass" column of Table 1 when the mass of the coating film immediately after application of the curable resin composition is converted to 100.

As can be seen from the values shown in Table 1, although the quality of the coating film after drying, pre-baking, and post-baking gradually decreases with the progress of the steps, the quality of the coating film after drying is higher than that of the comparison in each example.例者.

[Possibility of industrial application]

According to the present invention, it is possible to provide a curable resin composition which can form a cured film with high surface flatness. The cured film obtained from this curable resin composition is excellent in flatness, so it can be applied to displays and the like.

The diagrams in this case are all experimental data, which are not enough to represent the technical features of the invention claimed in the scope of the patent application in this case. Therefore, there is no designated representative diagram in this case.

Claims (12)

A curable resin composition containing a curable resin and a solvent, wherein the curable resin is a resin containing a copolymer having the following structural units: derived from unsaturated carboxylic acids and The structural unit of at least one monomer in the group consisting of unsaturated carboxylic anhydride, and the structural unit derived from a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond, the aforementioned solvent It contains a solvent with a boiling point of 200°C or higher and 300°C or lower, and the content of the aforementioned solvent with a boiling point of 200°C or higher is 20% by mass or higher of the total mass of the solvent in the curable resin composition. The curable resin composition described in the first item of the scope of the patent application contains a solvent having a boiling point of 220° C. or more and 300° C. or less that is 20% by mass or more of the total mass of the solvent in the curable resin composition. The curable resin composition described in item 1 or 2 of the scope of patent application, wherein the content of the solvent with a boiling point of 200°C or more and 300°C or less is 20% by mass of the total mass of the solvent in the curable resin composition Above and below 80% by mass. The curable resin composition described in item 1 or 2 of the scope of patent application, wherein the solvent having a boiling point of 200°C or more and 300°C or less is selected from 1,3-butanediol diacetate and 1,6-hexane At least one of the group consisting of glycol diacetate, 1,2,3-triacetoxypropane, and triethylene glycol monobutyl ether. The curable resin composition described in item 1 or 2 of the scope of the patent application further contains a solvent with a boiling point of 100°C or higher and less than 170°C. The curable resin composition described in item 5 of the scope of the patent application, wherein the solvent having a boiling point of 100°C or higher and less than 170°C is methoxybutanol, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetic acid Ester, propylene glycol monomethyl ether propionate or ethylene glycol monomethyl ether acetate. The curable resin composition described in item 5 of the scope of the patent application further contains a solvent with a boiling point of 170°C or higher and less than 200°C. The curable resin composition described in item 7 of the scope of patent application, wherein the solvents with a boiling point of 170°C or higher and less than 200°C are diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethyl ether Glycol ethyl methyl ether, dipropylene glycol dimethyl ether, or 3-methoxybutyl acetate. The curable resin composition described in item 1 or 2 of the scope of patent application, wherein the curable resin further contains a group selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins At least one of them. A method of manufacturing a cured film, comprising the steps of: coating the curable resin composition described in item 1 or 2 of the scope of the patent application on a substrate; and heating the coated curable resin composition step. According to the manufacturing method described in claim 10, the cured film is a color filter or a protective film for a touch panel. A display containing a cured film obtained by the manufacturing method described in item 10 of the scope of patent application.

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