TWI598391B - Curable resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition.

In a liquid crystal display panel or the like in recent years, a curable resin composition is used to form a photosensitive spacer or a protective layer. As such a curable resin composition, a composition containing only a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate as a resin is known (JP 2010-106154) -A).

In the case of the curable resin composition disclosed in the prior art, when the coating film formed by applying the curable resin composition on the substrate is placed in an environment of high temperature and high humidity, the adhesion between the coating film and the substrate exists. It may not be sufficient to satisfy the situation.

The present invention provides the following [1] to [5].

[1] A curable resin composition comprising (A), (B), and (C): (A)-based copolymers, which are derived from a group selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. At least one structural unit, and a structural unit derived from a monomer having an oxirane group and an ethylenically unsaturated bond; (B) is selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin At least one of the group consisting of: (C) is at least one compound selected from the group consisting of a polyvalent carboxylic anhydride and a polycarboxylic acid.

[2] The curable resin composition according to [1], which further comprises a member selected from the group consisting of A compound of at least one group consisting of a group consisting of an acryloyl group and a methacryl group.

[3] The curable resin composition according to [1] or [2], which further contains an antioxidant.

[4] A coating film formed by the curable resin composition according to any one of [1] to [3].

[5] A display device comprising the coating film of [4].

According to the present invention, it is possible to provide a curable resin composition which can produce a coating film having excellent adhesion to a substrate even when it is placed in an environment of high temperature and high humidity.

In the present specification, the compounds exemplified as the respective components may be used singly or in combination as long as they are not specifically stated.

The curable resin composition of the present invention comprises a copolymer (hereinafter sometimes referred to as "polymer (A)"), the copolymer comprising at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. A structural unit and a structural unit derived from a monomer having an oxirane group and an ethylenically unsaturated bond.

The polymer (A) is, for example, a polymer [A1] selected from at least one of the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a) "), a copolymer obtained by polymerizing a monomer (b) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); a polymer [A2]: a system thereof a), (b) and monomers copolymerizable with (a) and (b) (c) (wherein (a) and (b) are monomers which are different from each other) (hereinafter sometimes referred to as "(c)");

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid, Fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 , 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; 5-norbornene-2,3- Methyl dicarboxylate, 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- a carboxyl group-containing bicyclic unsaturated compound such as carboxyl-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4 -vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic acid Anhydride, bicyclo[2.2.1]hept-5-ene- Unsaturated dicarboxylic anhydrides such as 2,3-dicarboxylic anhydride (bicycloheptylene dicarboxylic anhydride); succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2- Unsaturated mono[(meth)acryloxyalkyl]esters of divalent or higher polycarboxylic acids such as (meth)acryloxyethyl]ester; such as α-(hydroxymethyl)acrylic acid The same molecule contains hydroxyl and carboxyl groups Unsaturated acrylates and the like.

Among these, acrylic acid, methacrylic acid, maleic anhydride, or the like can be preferably used in terms of copolymerization reactivity or alkali solubility.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The notation such as "(meth)acrylonitrile" and "(meth)acrylate" has the same meaning.

In the present invention, examples of the monomer (b) having an oxirane group and an ethylenically unsaturated bond include a structure obtained by epoxidizing an unsaturated chain aliphatic hydrocarbon and an ethylenically unsaturated bond. Monomer (b1) (hereinafter sometimes referred to as "(b1)"), or a monomer (b2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as Make "(b2)").

In the present invention, it is preferred that (b) is a monomer having an oxiranyl group and a (meth) acryloxy group. Further, it is preferable that (b) is (b2).

Specific examples of (b1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl group. Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-inter 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-tris(glycidoxymethyl) Styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris (glycidol) Oxymethyl)benzene The compound described in Japanese Laid-Open Patent Publication No. Hei 7-248625, etc., is a olefin, a 2,4,6-tris(glycidoxymethyl)styrene.

Examples of (b2) include ethylene oxide cyclohexene, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industries, Inc.), and 3,4-epoxy acrylate. Cyclohexyl methyl ester (for example, Cyclomer A400; manufactured by Daicel Chemical Industries Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries Co., Ltd.), formula (I) The compound represented by the formula, the compound represented by the formula (II), and the like.

In the formulae (I) and (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ¹ and X ² each independently represent a single ^{bond, -R 3 -, * - R} 3 -O -, * - R 3 -S -, * - R 3 -NH-.

R ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the key with O.

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

Examples of the hydroxyalkyl group include a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1-methyl group. Ethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxy Butyl and the like.

R ¹ and R ^{2 are} preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5- group. Dibasic, hexane-1,6-diyl and the like.

The X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylidene group, *-CH ₂ -O-, or *-CH ₂ CH ₂ -O-, and more preferably a single bond or * -CH ₂ CH ₂ -O-. Furthermore, * indicates a bond with O.

The compound represented by the formula (I) includes a compound represented by the formula (I-1) to the formula (I-15). Preferred are formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15). The compound represented by the formula (I-1), the formula (I-7), the formula (I-9), and the compound represented by the formula (I-15) are more preferred.

The compound represented by the formula (II) includes a compound represented by the formula (II-1) to the formula (II-15). Preferably, it is a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9), a formula (II-11) to a formula (II-15). The compound represented by the formula (II-1), the formula (11-7), the formula (II-9), and the compound represented by the formula (II-15) are more preferred.

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Further, these may be mixed at any ratio. In the case of mixing, the compounding ratio is preferably a compound represented by the formula (I): a compound represented by the formula (II) in a molar ratio of 5:95 to 95:5, more preferably 10: 90~90:10, and further preferably 20:80~80:20.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Alkyl (meth)acrylates such as tributyl ester; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ] decane-8-yl ester (in the technical field, known as dicyclopentanyl (meth) acrylate), trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] decene-8 - a base ester (referred to as a conventional name in the technical field, called (di) pentyl (meth) acrylate), dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate, etc. (A Cycloalkyl acrylates; phenyl (meth) acrylate, benzyl (meth) acrylate, etc. (aryl) aryl or arylalkyl esters; diethyl maleate, fumaric acid a dicarboxylic acid diester such as ethyl ester or diethyl itaconate; a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; [2.2.1] Hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-B Bicyclo[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-di(2'-hydroxyl Ethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]g 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-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1] Hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5 a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N -benzylmaleimide, N-butylimidazolyl-3-maleimide benzoate, N-butylimide-4-amine-4-maleimide butyrate N-butyl quinone imine-6-maleimide caproate, N-butyl quinone imine-3-maleimide propionate, N-(9-acridinyl) horse Dicarbonyl ruthenium derivatives such as phthalimide; styrenes such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene Acrylonitriles such as acrylonitrile and methacrylonitrile; vinyl compounds such as vinyl chloride, vinylidene chloride and vinyl acetate; acrylamides such as acrylamide and methacrylamide; Diene compounds such as olefin, isoprene, 2,3-dimethyl-1,3-butadiene; 3-methyl-3-methylpropenyloxymethyloxetane, 3 -methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxy Methyl oxetane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3- Ethyloxy-3-oxetane, 3-ethyl-3-propenyloxyethyloxetane, etc. ) Acrylate; tetrahydrofurfuryl acrylate (e.g., Viscoat V # 150, Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, tetrahydrofuryl acrylate and the like containing the (meth) acrylates.

Among these, styrene, dicyclopentenyl (meth)acrylate, N-phenylmaleimide, N-cyclohexyl horse are preferred in terms of copolymerization reactivity and alkali solubility. The imine, N-benzyl maleimide and bicyclo [2.2.1] hept-2-ene.

In the polymer [A1], the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the polymer [A1] is preferably in the range below.

Structural unit derived from (a): 5 to 60 mol% (more preferably 10 to 50 mol%)

Structural unit derived from (b): 40 to 95 mol% (more preferably 50 to 90 mol%)

When the ratio of the structural unit of the polymer [A1] is in the above range, the storage stability of the curable resin composition, the chemical resistance of the obtained coating film, heat resistance, and mechanical strength tend to be excellent.

The polymer [A1] can be referred to, for example, in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Chemical Co., Ltd., First Edition, 1st Brush, issued on March 1, 1972). Methods and fabrications are described in the literature.

Specifically, it is exemplified that a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction container, and oxygen is substituted by nitrogen gas, thereby stirring while performing a deoxidation atmosphere. Heating and insulation methods. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and can be used in any of those generally used in the field. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic In the solvent (E) which is a solvent (E) of the curable resin composition of the present invention, a solvent (such as benzamidine peroxide) can be used as the solvent.

Further, as the obtained copolymer, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, as the solvent in the polymerization, the solution after the reaction can be directly used for the preparation of the curable resin composition by using the same solvent as the solvent (E) described later, and the curable resin composition can be used. The manufacturing steps are simplified.

In the polymer [A2], the ratio of the structural unit derived from each monomer to the total number of moles of all the structural units constituting the polymer [A2] is preferably in the range below.

Structural unit derived from (a): 2 to 40 mol% (more preferably 5 to 35 mol%)

Structural unit derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol%)

Structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)

Further, the total amount of the structural unit derived from (a) and the structural unit derived from (b) is preferably 70 to 99 mol% with respect to the total number of moles of all structural units constituting the polymer [A2]. Good for 90~99 moles.

When the ratio of the structural unit of the polymer [A2] is in the above range, the storage stability of the curable resin composition, the chemical resistance of the obtained coating film, heat resistance, and mechanical strength tend to be excellent.

The polymer [A2] can be produced by the same method as the polymer [A1].

Specific examples of the polymer [A1] include a compound represented by (meth)acrylic acid/formula (I-1) (hereinafter sometimes referred to simply as "formula (I-1)". Formula (I-2), etc. Other similar) copolymer, (meth)acrylic acid / copolymer of formula (I-2), (meth)acrylic acid / copolymer of formula (I-3), (meth)acrylic acid / formula (I- 4) copolymer, (meth)acrylic acid / copolymer of formula (I-5), (meth)acrylic acid / copolymer of formula (I-6), (meth)acrylic acid / formula (I-7) Copolymer, (meth)acrylic acid / copolymer of formula (I-8), (meth)acrylic acid / copolymer of formula (I-9), copolymerization of (meth)acrylic acid / formula (I-10) a copolymer of (meth)acrylic acid/formula (I-11), a copolymer of (meth)acrylic acid/formula (I-12), a copolymer of (meth)acrylic acid/formula (I-13), (meth)acrylic acid / copolymer of formula (I-14), (meth)acrylic acid / copolymer of formula (I-15), (meth)acrylic acid / formula (II-1) Polymer, (meth)acrylic acid / copolymer of formula (II-2), (meth)acrylic acid / 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), Methyl)acrylic acid / copolymer of formula (II-8), (meth)acrylic acid / copolymer of formula (II-9), (meth)acrylic acid / copolymer of formula (II-10), (methyl Acrylic acid / copolymer of formula (II-11), (meth)acrylic acid / copolymer of formula (II-12), (meth)acrylic acid / copolymer of formula (II-13), (meth)acrylic acid / copolymer of the formula (II-14), (meth)acrylic acid / copolymer of the formula (II-15), (meth)acrylic acid / copolymer of the formula (I-1) / formula (II-1), (Meth)acrylic acid / copolymer of formula (I-2) / formula (II-2), (meth)acrylic acid / copolymer of formula (I-3) / formula (II-3), (methyl) Acrylic acid / copolymer of formula (I-4) / formula (II-4), (meth)acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth)acrylic acid / formula ( I-6) / copolymer of formula (II-6), (meth)acrylic acid / copolymer of formula (I-7) / formula (II-7), (meth)acrylic acid / formula (I-8) /Formula (II-8) Polymer, (meth)acrylic acid / copolymer of formula (I-9) / formula (II-9), (meth)acrylic acid / copolymer of formula (I-10) / formula (II-10), Methyl)acrylic acid / copolymer of formula (I-11) / formula (II-11), (meth)acrylic acid / copolymer of formula (I-12) / formula (II-12), (meth)acrylic acid / copolymer of the formula (I-13) / formula (II-13), (meth)acrylic acid / copolymer of the formula (I-14) / formula (II-14), (meth)acrylic acid / formula (I -15) / copolymer of the formula (II-15), (meth)acrylic acid / copolymer of the formula (I-1) / formula (I-7), (meth)acrylic acid / formula (I-1) / Copolymer of formula (II-7), copolymer of crotonic acid / formula (I-1), copolymer of crotonic acid / formula (I-2), copolymerization of crotonic acid / formula (I-3) , crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5), crotonic acid / copolymer of formula (I-6), butene Acid / copolymer of formula (I-7), copolymer of crotonic acid / formula (I-8), copolymer of crotonic acid / formula (I-9), crotonic acid / formula (I-10) Copolymer, crotonic acid / copolymer of formula (I-11), crotonic acid / copolymer of formula (I-12), crotonic acid / copolymer of formula (I-13), crotonic acid / Copolymer of formula (I-14), copolymer of crotonic acid / formula (I-15), copolymer of crotonic acid / formula (II-1), copolymerization of crotonic acid / 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 / formula ( a copolymer of II-6), a copolymer of crotonic acid / formula (II-7), a copolymer of crotonic acid / formula (II-8), a copolymer of crotonic acid / formula (II-9), Butenoic acid / copolymer of formula (II-10), copolymer of caudonic acid / formula (II-11), copolymer of crotonic acid / formula (II-12), crotonic acid / formula (II- 13) copolymer, butenoic acid / copolymer of formula (II-14), crotonic acid / copolymer of formula (II-15), maleic acid / copolymer of formula (I-1), Malay Acid / copolymer of formula (I-2), copolymer of maleic acid / formula (I-3), copolymer of maleic acid / formula (I-4), maleic acid / formula (I-5) Copolymer, maleic acid / formula (I-6) Polymer, maleic acid / copolymer of formula (I-7), copolymer of maleic acid / formula (I-8), copolymer of maleic acid / formula (I-9), maleic acid / formula Copolymer of (I-10), copolymer of maleic acid/formula (I-11), copolymer of maleic acid/formula (I-12), copolymer of maleic acid/formula (I-13) , maleic acid / copolymer of formula (I-14), copolymer of maleic acid / formula (I-15), copolymer of maleic acid / formula (II-1), maleic acid / formula (II -2) copolymer, maleic acid / copolymer of formula (II-3), copolymer of maleic acid / formula (II-4), copolymer of maleic acid / formula (II-5), horse Copolymer / copolymer of formula (II-6), copolymer of maleic acid / formula (II-7), copolymer of maleic acid / formula (II-8), maleic acid / formula (II-9 Copolymer, maleic acid / copolymer of formula (II-10), maleic acid / formula Copolymer of (II-11), copolymer of maleic acid/formula (II-12), copolymer of maleic acid/formula (II-13), copolymer of maleic acid/formula (II-14) , maleic acid / copolymer of formula (II-15), (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1), (meth)acrylic acid / maleic anhydride / formula (I-2 Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-3), (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 / formula (I-7 Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-9), (meth)acrylic acid /Maleic 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/copolymer of formula (I-14), (meth)acrylic acid /Maleic anhydride / copolymer of formula (I-15), (meth)acrylic acid / horse Anhydride/copolymer of formula (II-1), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-2), copolymerization of (meth)acrylic acid/maleic anhydride/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/Malay Anhydride/copolymer of formula (II-6), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-7), copolymerization of (meth)acrylic acid/maleic anhydride/formula (II-8) , (meth)acrylic acid/maleic anhydride/copolymer of formula (II-9), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-10), (meth)acrylic acid/Malay Anhydride/copolymer of formula (II-11), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-12), copolymerization of (meth)acrylic acid/maleic anhydride/formula (II-13) , (meth)acrylic acid / Malay An acid anhydride/copolymer of the formula (II-14), a copolymer of (meth)acrylic acid/maleic anhydride/formula (II-15), and the like.

Specific examples of the polymer [A2] include a copolymer of (meth)acrylic acid/methyl (I-1)/(meth)acrylate, and (meth)acrylic acid/(I-2)/( Copolymer of methyl methacrylate, copolymer of (meth) acrylate / methyl (I-3) / methyl (meth) acrylate, (meth) acrylate / formula (I-4) / (methyl a copolymer of methyl acrylate, a copolymer of (meth)acrylic acid/methyl (I-5)/(meth)acrylate, (meth)acrylic acid/(I-6)/(meth)acrylic acid Copolymer of methyl ester, (meth)acrylic acid / copolymer of methyl (I-7) / (meth) acrylate, (meth) acrylate / methyl (I-8) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of formula (I-9) / methyl (meth) acrylate, copolymerization of (meth) acrylate / methyl (I-10) / (meth) acrylate a copolymer of (meth)acrylic acid/methyl (I-11)/methyl (meth)acrylate, a copolymer of (meth)acrylic acid/methyl (I-12)/(meth)acrylate, Copolymer of (meth)acrylic acid/methyl (I-13)/(meth)acrylate, copolymer of (meth)acrylic acid/methyl (I-14)/(methyl)acrylate, (A) Acrylic acid / formula (I-15) / (meth) propylene Copolymer of methyl ester, copolymer of (meth)acrylic acid/methyl (II-1)/methyl (meth)acrylate, (meth)acrylic acid / formula (II-2) / (meth)acrylic acid Copolymer of ester, (meth)acrylic acid / copolymer of methyl (II-3) / methyl (meth)acrylate, (meth)acrylic acid / methyl (II-4) / methyl (meth)acrylate Copolymer, (meth)acrylic acid / copolymer of methyl (II-5) / methyl (meth)acrylate, copolymer of (meth)acrylic acid / methyl (II-6) / methyl (meth)acrylate , (meth)acrylic acid / copolymer of formula (II-7) / methyl (meth) acrylate a copolymer of (meth)acrylic acid/methyl (II-8)/methyl (meth)acrylate, a copolymer of (meth)acrylic acid/methyl (II-9)/methyl (meth)acrylate, Copolymer of (meth)acrylic acid/methyl (II-10)/methyl (meth)acrylate, copolymer of (meth)acrylic acid/methyl (II-11)/methyl (meth)acrylate, (A) Acrylic acid / copolymer of formula (II-12) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-13) / methyl (meth) acrylate, (methyl) Acrylic acid / copolymer of (II-14) / methyl (meth) acrylate, (meth) acrylic / copolymer of (II-15) / methyl (meth) acrylate, (meth) acrylic / Copolymer of (I-1) / (meth)acrylic acid dicyclopentanyl ester, (meth)acrylic acid / copolymer of formula (II-1) / dicyclopentanyl (meth)acrylate, (meth)acrylic acid / Copolymer of formula (I-1) / formula (II-1) / (meth)acrylic acid dicyclopentanyl ester, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth)acrylate, horse Copolymer of acid/(I-1)/dicyclopentanyl (meth)acrylate, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (I-1)/(meth)acrylate , (meth)acrylic acid / formula (I-1) Copolymer of methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, copolymer of crotonic acid / dicyclopentanyl (II-1) / (meth) acrylate, maleic acid / formula ( II-1)/Copolymer of dicyclopentanyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/dicyclopentanyl (meth)acrylate, (methyl) Acrylic acid / copolymer of (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, (meth) acrylate / phenyl (I-1) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of phenyl (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / (methyl Copolymer of phenyl acrylate, copolymer of crotonic acid / phenyl (I-1) / phenyl (meth) acrylate, copolymerization of maleic acid / phenyl (I-1) / (meth) acrylate , (meth)acrylic acid / maleic anhydride / a copolymer of the formula (I-1)/phenyl (meth)acrylate, a copolymer of (meth)acrylic acid/methyl (I-1)/methyl (meth)acrylate/phenyl (meth)acrylate, Butenoic acid / copolymer of phenyl (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / phenyl (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / Maleic anhydride / copolymer of phenyl (II-1) / phenyl (meth) acrylate, (meth) acrylate / methyl (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / copolymer of formula (II-1) / diethyl maleate, (Meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / diethyl maleate, copolymer of crotonic acid / formula (I-1) / diethyl maleate , maleic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1) / diethyl maleate, ( Methyl)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / diethyl maleate, copolymer of crotonic acid / formula (II-1) / diethyl maleate , maleic acid / copolymer of formula (II-1) / diethyl maleate, (meth)acrylic acid / horse Acetic acid anhydride / copolymer of formula (II-1) / diethyl maleate, copolymer of (meth)acrylic acid / methyl (II-1) / methyl (meth)acrylate / diethyl maleate , (meth)acrylic acid / copolymer of 2-hydroxyethyl (I-1) / (meth) acrylate, (meth) acrylate / 2-hydroxyethyl (II-1) / (meth) acrylate Copolymer of ester, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth)acrylate, butenoic acid / formula (I-1) / Copolymer of 2-hydroxyethyl (meth)acrylate, copolymer of maleic acid / 2-hydroxyethyl (I-1)/(meth)acrylate, (meth)acrylic acid/maleic anhydride/form Copolymer of (I-1)/(2-hydroxyethyl)(meth)acrylate, (meth)acrylic acid/methyl (I-1)/(meth)acrylate/2-hydroxyethyl (meth)acrylate Copolymer of ester, crotonic acid / 2-hydroxyethyl (II-1) / 2-hydroxyethyl (meth)acrylate Polymer, maleic acid / copolymer of formula (II-1) / 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / maleic anhydride / formula (II-1) / (meth)acrylic acid Copolymer of 2-hydroxyethyl ester, (meth)acrylic acid/copolymer of formula (II-1)/methyl (meth)acrylate/2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/ a copolymer of the formula (I-1)/bicyclo[2.2.1]hept-2-ene, a copolymer of (meth)acrylic acid/formula (II-1)/bicyclo[2.2.1]hept-2-ene, (Meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula (I-1) / bicyclo [2.2. 1] copolymer of hept-2-ene, maleic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / maleic anhydride / formula (I -1)/bicyclo[2.2.1]Hept-2-ene copolymer, (meth)acrylic acid/(I-1)/(meth)acrylic acid methyl ester/bicyclo[2.2.1]heptan-2- Copolymer of olefin, crotonic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (II-1) / bicyclo [2.2.1] g Copolymer of 2-alkenyl, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/bicyclo[2.2.1]hept-2-ene, (meth)acrylic acid/formula (II-1) ) / (methyl) acrylate / bicyclo [2.2.1] G Copolymer of 2-ene, copolymer of (meth)acrylic acid/(I-1)/N-cyclohexylmaleimine, (meth)acrylic acid/(II-1)/N-ring Copolymer of hexylmaleimide, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / N-cyclohexyl maleimide, butenoic acid / formula (I -1) /N-cyclohexylmaleimide copolymer, maleic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide, (meth)acrylic acid / maleic anhydride Copolymer of formula (I-1)/N-cyclohexylmaleimine, (meth)acrylic acid/methyl (I-1)/(meth)acrylate/N-cyclohexylmalaya Copolymer of amine, butenoic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide, maleic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, (meth)acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmalay Copolymer of quinone imine, (meth)acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, (meth) acrylate / formula (I -1) / copolymer of styrene, (meth)acrylic acid / copolymer of formula (II-1) / styrene, (meth)acrylic acid / formula (I-1) / formula (II-1) / benzene Copolymer of ethylene, copolymer of butenoic acid / formula (I-1) / styrene, copolymer of maleic acid / formula (I-1) / styrene, (meth) acrylic acid / maleic anhydride / formula (I-1)/styrene copolymer, (meth)acrylic acid/copolymer of formula (I-1)/methyl (meth)acrylate/styrene, crotonic acid/formula (II-1)/ Copolymer of styrene, copolymer of maleic acid / formula (II-1) / styrene, copolymer of (meth)acrylic acid / maleic anhydride / formula (II-1) / styrene, (methyl) Copolymer of Acrylic/(II-1)/Methyl (meth)acrylate/styrene, copolymerization of (meth)acrylic acid/(I-1)/N-cyclohexylmaleimide/styrene , (meth)acrylic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, (meth)acrylic acid / formula (I-1) / formula (II-1) /N-cyclohexylmaleimide/styrene copolymer, crotonic acid / formula (I-1) / N Copolymer of cyclohexylmaleimide/styrene, copolymer of maleic acid/(I-1)/N-cyclohexylmaleimide/styrene, (meth)acrylic acid/Malay Anhydride / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth)acrylic acid / methyl (I-1) / methyl (meth)acrylate / N-cyclohexyl Copolymer of maleic imine/styrene, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / formula (II-1) / Copolymer of N-cyclohexylmaleimide/styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/N-cyclohexylmaleimide/styrene, Methyl)acrylic acid/copolymer of the formula (II-1)/(meth)acrylic acid/N-cyclohexylmaleimide/styrene, and the like.

The polystyrene-equivalent weight average molecular weight of the polymer (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight of the polymer (A) is in the above range, the coating property of the curable resin composition tends to be good.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer (A) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above range, the obtained coating film tends to have excellent chemical resistance.

The acid value of the polymer (A) is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 50 mg- KOH/g or more and 135 mg-KOH/g or less. Here, the acid value is a value measured by the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the polymer, and can be determined by titration with an aqueous potassium hydroxide solution. When the acid value of the polymer (A) is in the above range, the obtained coating film tends to have excellent adhesion to the substrate.

The content of the polymer (A) is preferably from 50 to 99% by mass, more preferably from 60 to 95% by mass, based on the total amount of the polymer (A) in the epoxy resin (B). When the content of the polymer (A) is in the above range, the obtained coating film tends to have excellent adhesion to the substrate.

The curable resin composition of the present invention contains at least one epoxy resin (B) selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins (hereinafter sometimes referred to as "epoxy resin ( B)").

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether group, and can be produced by reacting a phenol or a polyhydric alcohol with epichlorohydrin.

Specific examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, and o-cresol. A novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin, or the like.

The glycidyl ester type epoxy resin can be produced by reacting a phthalic acid derivative or a carbonyl group such as a fatty acid with epichlorohydrin.

Examples of the glycidyl ester type epoxy resin include a glycidyl ester type epoxy resin derived from an aromatic carboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid or terephthalic acid.

The epoxy resin (B) used in the curable resin composition of the present invention is preferably an aromatic epoxy resin, preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolak type ring. A glycidyl ether type epoxy resin such as an oxygen resin, an o-cresol novolak type epoxy resin, or a polyphenol type epoxy resin. Among them, a bisphenol A type epoxy resin is particularly preferred.

The glycidyl ether type epoxy resin as described above can be produced by condensing a corresponding phenol with epichlorohydrin in the presence of a strong base by a conventionally known method. This reaction can be carried out by a prior method known to the manufacturer. Further, a commercially available product can also be used. As a commercial item of the bisphenol A type epoxy resin, for example, jER157S70, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (manufactured by Mitsubishi Chemical Corporation) can be used. Wait. As a commercial item of the bisphenol F-type epoxy resin, for example, Epikote 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Tohto Kasei Co., Ltd.), or the like can be used. Phenolic novolac type epoxy tree As a commercial product of the fat, for example, Epikote 152, Epikote 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), and DEN-438 (manufactured by Dow Chemical Co., Ltd.) can be used. Wait. As a commercial product of an o-cresol novolac type epoxy resin, for example, EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.) can be used. )Wait. As a commercial item of a polyphenol type epoxy resin, for example, Epikote 1032H60, Epikote YX-4000 (made by Mitsubishi Chemical Corporation), etc. can be used.

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

The acid value of the epoxy resin (B) is usually less than 30 mg-KOH/g, more preferably 10 mg-KOH/g or less.

Further, the weight average molecular weight of the epoxy resin (B) is preferably from 300 to 10,000, more preferably from 400 to 6,000, still more preferably from 500 to 4,800.

The content of the epoxy resin (B) is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, based on the total amount of the polymer (A) and the epoxy resin (B). When the content of the polymer (A) is in the above range, the obtained coating film tends to have excellent adhesion to the substrate.

Further, the total content of the polymer (A) and the epoxy resin (B) is preferably from 50 to 98% by mass, and more preferably from 55 to 85% by mass, based on the solid content of the curable resin composition. If the total content is in the above range, the resulting The coating film has a tendency to be excellent in chemical resistance. Here, the solid content component of the curable resin composition means the amount of the solvent (E) removed from the curable resin composition.

The curable resin composition of the present invention contains at least one compound selected from the group consisting of a polyvalent carboxylic anhydride and a polyvalent carboxylic acid (hereinafter sometimes referred to as "compound (C)"). The polyvalent carboxylic acid is a compound having two or more carboxyl groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The compound (C) preferably has a molecular weight of 3,000 or less, more preferably 1,000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, and 2-(2oct-3-enyl)amber. Anhydride, chain of 2-(2,4,6-trimethylindol-3-enyl) succinic anhydride, 1,2,3-propanetricarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Polycarboxylic acid anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrogen 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 anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (bicycloheptene dicarboxylic anhydride), methylbicyclo[2.2.1]hept-5 - an alicyclic polycarboxylic acid anhydride such as alkene-2,3-dicarboxylic anhydride or cyclopentane tetracarboxylic dianhydride; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic acid Anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, ethylene glycol double (dehydrated benzene triacetate) Acid ester) Alcohol three (dehydrated trimellitate), glycerol double (dehydration) Trimelliate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene [1,2 -c] an aromatic polycarboxylic acid anhydride such as furan-1,3-diketone;

ADEKA HARDENER-EH-700 (trade name (the same below), manufactured by ADEKA Co., Ltd.), RIKACID-HH, RIKACID-TH, RIKACID-MH, RIKACID-MH-700 (manufactured by Nippon Chemical and Chemical Co., Ltd.) Commercial products such as EPIKURE 126, EPIKURE YH-306, and EPIKURE DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.).

Examples of the polyvalent carboxylic acid include chain polycarboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and a polycarboxylic acid derived from a chain-like polycarboxylic acid anhydride; An alicyclic polycarboxylic acid such as hexane dicarboxylic acid or a polycarboxylic acid derived from an alicyclic polycarboxylic acid anhydride; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and a derivative aromatic An aromatic polycarboxylic acid such as a polyvalent carboxylic acid of a polyvalent carboxylic anhydride;

These polyvalent carboxylic anhydrides and polycarboxylic acids may be used singly or in combination of two or more.

Among them, the chain carboxylic acid anhydride and the alicyclic polycarboxylic acid anhydride are more preferable, and the alicyclic polycarboxylic acid anhydride is more preferable because the heat resistance of the coating film is excellent, and in particular, the transparency in the visible light region is hard to be lowered.

The content of the compound (C) in the curable resin composition of the present invention is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on 100 parts by mass of the polymer (A). If the content of the compound (C) is within the above range, there is a coating film It is excellent in heat resistance and adhesion, and even when a coating film is formed on a substrate having minute impurities, it is difficult to produce a coating film which is concentrically enlarged from the minute impurities and is excellent in chemical resistance. tendency.

It is preferred that the curable resin composition of the present invention contains an antioxidant (D). Examples of the antioxidant (D) include 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate. 2-[1-(2-hydroxy-3,5-di-third-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 6-[3-(3- Third butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2] Two [mouth + 咢] phosphocycloheptane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}-1,1 -Dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol) 4,4'-butylidene bis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2 '-Thiobis(6-tert-butyl-4-methylphenol), 3,3'-dithiolongate dilaurate, 3,3'-thiodipropionate dimyristate, 3 , 3'-distearyl thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), 1,3,5-tris(3,5-di-t-butyl-4-hydroxyl Benzyl)-1,3,5-three -2,4,6(1H,3H,5H)-Trione, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(both Trimethyl-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,6- Di-tert-butyl-4-methylphenol, etc. Commercial products such as IRGANOX 3114 (manufactured by Ciba Japan Co., Ltd.) can also be used.

The content of the antioxidant (D) is usually 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.5 parts by mass or more, based on 100 parts by mass of the polymer (A). The amount is below. When the content of the antioxidant (D) is within the above range, the obtained coating film tends to have excellent heat resistance and pencil hardness. When the content of the antioxidant (D) exceeds the above range, the pencil hardness of the coating film is lowered.

It is preferred that the curable resin composition of the present invention contains a compound having at least one group selected from the group consisting of an acryloyl group and a methacryl group (hereinafter sometimes referred to as "(meth)acryloyl group"). (F) (hereinafter sometimes referred to as "(meth) propylene compound (F)"). When the curable resin composition of the present invention contains the (meth) propylene compound (F), the hardness and chemical resistance of the coating film tend to be improved.

The (meth) propylene compound (F) having one (meth) acrylonitrile group may be the same as those exemplified as the above (a), (b) and (c), and among them, ( Methyl) acrylate.

Examples of the (meth) propylene compound (F) having two (meth) acrylonitrile groups include 1,3-butanediol di(meth) acrylate and 1,3-butylene diol (methyl group). Acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether , ethoxylated bisphenol A di(meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3- Methyl pentanediol di(meth) acrylate or the like.

Examples of the (meth) propylene compound (F) having three or more (meth) acrylonitrile groups include trimethylolpropane tri(meth) acrylate and pentaerythritol. (Meth) acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth) acrylate, ethoxylated trimethylolpropane tri(meth) acrylate, propoxylated three Hydroxymethylpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate , tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and Reaction of anhydride, reaction of dipentaerythritol penta (meth) acrylate with anhydride, reaction of tripentaerythritol hepta (meth) acrylate with anhydride, caprolactone modified trimethylolpropane tri(methyl) Acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol IV (Meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, Modified dipentaerythritol hexa(meth) acrylate, caprolactone modified tripellitate tetra(meth) acrylate, caprolactone modified tripellitate pentoxide (meth) acrylate, caprolactone modified tripellitate (Meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate A reaction product with an acid anhydride, a reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate with an acid anhydride, a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, and the like.

The (meth) propylene compound (F) is preferably a (meth) propylene compound (F) having three or more (meth) acrylonitrile groups, more preferably dipentaerythritol. (Meth) acrylate.

The content of the (meth) propylene compound (F) is preferably 20 to 100 parts by mass, more preferably 25 to 70 parts by mass, per 100 parts by mass of the polymer (A). When the content of the (meth) propylene compound (F) is in the above range, the smoothness, reliability, and mechanical strength of the obtained coating film tend to be good.

The curable resin composition of the present invention preferably contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be derived from an ester solvent (a solvent containing -COO-, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (containing in the molecule - a COO-and a solvent of -O-), a ketone solvent (a solvent containing -CO- in a molecule, a solvent containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, a dimethyl hydrazine, etc. use.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran , tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, Methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

As a guanamine solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl. Pyrrolidone and the like.

These solvents may be used singly or in combination of two or more.

Among the above solvents, in terms of coatability and dryness, it is preferably 1 The organic solvent at the boiling point of atm is 120 ° C or more and 180 ° C or less. Among them, preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and the like. Mix the solvent.

The content of the solvent (E) in the curable resin composition is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass based on the curable resin composition. In other words, the solid content of the curable resin composition is preferably from 5 to 40% by mass, more preferably from 5 to 30% by mass. When the content of the solvent (E) is in the above range, the film coated with the curable resin composition tends to have high flatness.

The curable resin composition of the present invention may also contain a surfactant (G). Examples of the surfactant include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant containing a fluorine atom.

As the polyoxymethylene surfactant, a surfactant containing a ruthenium oxygen bond can be mentioned.

Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Polyoxygenated Oil SH8400 (trade name, Dow Corning Toray) Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Made by Japan Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain.

Specifically, Fluorinert (registered trademark) FC430, Fluorinert FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (DIC) Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd.) Co., Ltd.), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), etc.

Examples of the polyfluorene-based surfactant containing a fluorine atom include a surfactant having a ruthenium oxygen bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC Corporation), and the like. Preferably, Megafac (registered trademark) F475 is mentioned.

The surfactant (G) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less based on the curable resin composition. By including a surfactant in this range, the flatness of the coating film can be improved.

The curable resin composition of the present invention may contain a filler, another polymer compound, a thermal radical generator, and ultraviolet absorption as needed. Additives such as a agent, a chain transfer agent, an adhesion promoting material, and a hardening accelerator.

Examples of the filler include glass, cerium oxide, aluminum oxide, and the like.

Examples of the other polymer compound include thermosetting resins such as maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyamine. A thermoplastic resin such as an acid ester.

Specific examples of the thermal radical generating agent include 2,2'-azobis(2-methylvaleronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). .

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and 3-glycidoxy propyl trimethoxy. Decane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxy Propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-sulfonylpropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, N-2-(aminoethyl) --3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, N-2-(aminoethyl) --3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxydecane, 3 -Aminopropyltriethoxydecane, N- Phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, and the like.

Examples of the hardening accelerator include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, and 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-methyl Imidazole, 1-cyanomethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and the like.

The curable resin composition of the present invention does not substantially contain a photopolymerization initiator. That is, in the curable resin composition of the present invention, the content of the photopolymerization initiator relative to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass. As a photopolymerization initiator, an alkylphenone compound, three A compound, a mercaptophosphine oxide compound, an anthracene compound, and the like.

Further, the curable resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. That is, in the curable resin composition of the present invention, the content of the colorant relative to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

Further, the curable resin composition of the present invention is used in a quartz cuvette filled to an optical path length of 1 cm, and a spectrophotometer is used at the measurement wavelength. When the transmittance is measured under conditions of 400 to 700 nm, the average transmittance is preferably 70% or more, more preferably 80% or more.

When the curable resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The average transmittance is a coating film having a thickness of 3 μm after heat hardening (for example, 100 to 250 ° C for 5 minutes to 3 hours), and is carried out using a spectrophotometer at a measurement wavelength of 400 to 700 nm. The average of the conditions measured. Thereby, a coating film excellent in transparency in the visible light region can be provided.

The curable resin composition of the present invention can be obtained by copolymerizing the copolymer (A), the epoxy resin (B) and the compound (C), and optionally the (meth) propylene compound (F) by a conventionally known method. The solvent (E) and other components are produced by stirring and mixing. Preferably, the mixture is filtered by a filter having a pore diameter of about 0.05 to 1.0 μm after mixing.

The curable resin composition of the present invention is applied onto a substrate and cured by heat, whereby a coating film can be produced.

Examples of the substrate include glass, metal, plastic, and the like, and a color filter, various insulating films, conductive films, and a driving circuit can be formed on the substrate.

It is preferred to use the various coating devices such as a spin coater, a slit type & spin coater, a slit coater, an ink jet machine, a roll coater, and a dip coater to harden the present invention. The resin composition is coated on a substrate.

It is preferred to carry out vacuum drying or prebaking after coating to remove volatile components such as a solvent.

Preferably, the coating film from which the volatile component is removed is at 150 to 240 ° C After baking for 10 to 120 minutes, a coating film can be formed.

The coating film obtained in the above manner can be used, for example, as a protective layer for a liquid crystal display device, an organic EL (Electro Luminescence) display device, or an electronic paper. Moreover, it can also be used for a member for a display device such as a touch panel. According to the present invention, it is possible to realize a display device having a high-quality coating film produced at a high yield.

Example

Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise marked.

Synthesis Example 1

Nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1) are represented. A mixture of the compounds, molar ratio = 50:50) 360 parts by mass was dissolved in 190 parts by mass of diethylene glycol ethyl methyl ether to prepare a solution. The resulting solution was added dropwise to a flask maintained at 70 ° C over 4 hours using a drip pump.

On the other hand, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in 240 parts by mass of diethylene glycol ethyl methyl ether, and the obtained The solution was added dropwise to the flask over 5 hours using an additional drop pump. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer of solid content of 42.6 mass% and acid value of 60 mg-KOH/g (solid content conversion). A solution of the substance (resin Aa). The obtained resin Aa had a weight average molecular weight (Mw) of 8.0 × 10 ³ and a molecular weight distribution (Mn / Mw) of 1.91.

Synthesis Example 2

Nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added. Heat to 70 ° C while stirring. Then, 60 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1)) a mixture of 50:50 in molar ratio) 240 parts of 3-methoxybutyl acetate was prepared to prepare a solution, and the solution was added dropwise to a temperature of 70 ° C over 4 hours using a dropping funnel. Inside the flask.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate, and the resulting solution was used in addition. The dropping funnel was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer having a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content). A solution of (Resin Ab). The obtained resin Ab had a weight average molecular weight Mw of 1.34 × 10 ⁴ and a molecular weight distribution (Mn/Mw) of 2.50.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resins Aa and Ab were measured under the following conditions using a GPC (gel permeation chromatography) method.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI (Refractive Index, refractive index)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

(Examples 1 to 7 and Comparative Examples 1 to 2)

The composition of Table 1 was mixed to obtain a curable resin composition.

Epoxy resin (B): bisphenol A type epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Corporation)

Compound (C1): 1,2,3,6-tetrahydrophthalic anhydride (RIKACID TH; manufactured by Nippon Chemical and Chemical Co., Ltd.; compound represented by the following formula)

Compound (C2): hexahydrophthalic anhydride (RIKACID HH; manufactured by New Japan Physical and Chemical Co., Ltd.; compound represented by the following formula)

Compound (C3): 4-methylhexahydrophthalic anhydride (RIKACID MH; manufactured by Nippon Chemical and Chemical Co., Ltd.; compound represented by the following formula)

Compound (C4): 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.; compound represented by the following formula)

Compound (C5): trimellitic anhydride (manufactured by Kanto Chemical Co., Ltd.)

Antioxidant (D): 1,3,5-tris(4-hydroxy-3,5-di-t-butylbenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione (IRGANOX3114; manufactured by Ciba Japan Co., Ltd.)

(Meth) propylene compound (F): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Surfactant (G): Polyether modified polyoxyxide oil (manufactured by Dow Corning Toray Co., Ltd.; SH8400)

Polymerization initiator (H1): Cb; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; Made by Baotu Valley Chemical Co., Ltd.)

Polymerization initiation aid (H2): C2a; 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline

Polymerization start aid (H3): pentaerythritol tetrapropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

<The penetration rate of the composition>

UV-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cuvette, optical path length; 1 cm), respectively, in the 400-700 nm of the obtained curable resin composition The average transmittance (%) was measured. The results are shown in Table 2.

<Methods of Producing Coating Films of Examples 1 to 7 and Comparative Example 1>

A 2 inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, followed by drying. The curable resin composition was spin-coated on the glass substrate in such a manner that the film thickness after baking was 2.0 μm, and then prebaked at 90 ° C for 10 minutes in a clean oven. Thereafter, it was heated at 230 ° C for 40 minutes to obtain a film.

<Method for Producing Coating Film of Comparative Example 2>

A 2 inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. The curable resin composition was exposed at an exposure amount (405 nm) of 200 mJ/cm ² , and was spin-coated on the glass substrate in such a manner that the film thickness after development, water washing, and post-baking reached 2.0 μm, and then Prebaking at 90 ° C for 3 minutes in a clean oven. After cooling, the coating was cured in an atmosphere using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.; light source: ultrahigh pressure mercury lamp) at an exposure amount of 100 mJ/cm ² (405 nm basis). The substrate of the resin composition is irradiated with light. In addition, the irradiation of the curable resin composition at this time is performed by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Laser Co., Ltd.) and using light of 400 nm or less. After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for development, washing with water, and then at 220 ° C in an oven. It was heated for 20 minutes to obtain a film.

<Average penetration rate of coating film>

The transmittance (%) in 400 nm of the obtained coating film and the average transmittance (%) in 400 to 700 nm were measured using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 2.

<heat resistance>

The obtained coating film was heat-treated at 240 ° C for 4 hours, and the transmittance at 400 nm before and after heating was measured, and the change in transmittance (%) was determined according to the following formula. The closer to 100%, the smaller the color or discoloration of the coating film before and after heating. The results are shown in Table 2.

Change in penetration rate (%): (penetration rate after heating (%) / penetration rate before heating (%)) × 100

<Adhesiveness>

A coating film was formed on a glass substrate with ITO by performing the same operation as described above except that the glass substrate was replaced with a glass substrate with ITO. The coating film was subjected to a pressure cooker test (temperature 120 ° C, humidity 100%, pressure 2 atm; saturated pressure cooker PC-305S; manufactured by Hirayama Manufacturing Co., Ltd.) 2 hours later, with 8.3.7 of JIS K-5400-1990 The adhesion of the coating film to the glass substrate with ITO was evaluated by the adhesive mesh tape method. The number of meshes remaining on the substrate in the grid 100 is referred to as adhesion (part), and is shown in Table 2.

As shown in Table 2, it was confirmed that the coating film obtained from the curable resin composition of the present invention containing the compound (C) is excellent in adhesion to a substrate even in a high-temperature, high-humidity environment.

By using the coating film formed from such a curable resin composition, a display device excellent in durability can be produced.

According to the present invention, it is possible to provide a curable resin composition which can produce a coating film having excellent adhesion to a substrate even when it is placed in an environment of high temperature and high humidity.

Claims (5)

A curable resin composition comprising (A), (B) and (C): (A) copolymer comprising at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides a structural unit, and a structural unit derived from a monomer having an oxirane group and an ethylenically unsaturated bond; (B) is selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin At least one of (C) is at least one selected from the group consisting of a polyvalent carboxylic anhydride and a polycarboxylic acid. The curable resin composition of claim 1, which further comprises a compound having at least one selected from the group consisting of an acryloyl group and a methacryl group. The curable resin composition of claim 1 or 2, which further comprises an antioxidant. A coating film formed by the curable resin composition according to any one of claims 1 to 3. A display device comprising the coating film of claim 4.