JP6019774B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

In recent liquid crystal display panels and the like, a curable resin composition is used to form a photo spacer and an overcoat. 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. (Patent Document 1).

JP 2010-106154 A

  In the conventionally proposed curable resin composition, when a coating film formed by applying the curable resin composition to a substrate is placed in a high-temperature and high-humidity environment, the adhesion between the coating film and the substrate is reduced. However, there were cases where it was not always satisfactory.

The present invention provides the following [1] to [5].
[1] A curable resin composition containing (A), (B) and (C).
(A) a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer having an oxiranyl group and an ethylenically unsaturated bond. Copolymer (B) at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (C) at least one type selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid Compound [2] The curable resin composition according to [1], further comprising a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.
[3] The curable resin composition according to [1] or [2], further comprising an antioxidant.
[4] A coating film formed from the curable resin composition according to any one of [1] to [3].
[5] A display device comprising the coating film according to [4].

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

  In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination.

  The curable resin composition of the present invention is a monomer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, an oxiranyl group, and an ethylenically unsaturated bond And a copolymer containing a structural unit derived from (hereinafter sometimes referred to as “polymer (A)”).

As the polymer (A), for example,
Polymer [A1]: at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), an oxiranyl group and an ethylenically unsaturated group. A copolymer obtained by polymerizing a monomer (b) having a saturated bond (hereinafter sometimes referred to as “(b)”);
Polymer [A2]: (a) and (b), monomer (c) copolymerizable with (a) and (b) (however, a monomer different from (a) and (b)) (Hereinafter, referred to as “(c)” in some cases).
Etc.

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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-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- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride (hymic anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

In the present invention, examples of the monomer (b) having an oxiranyl group and an ethylenically unsaturated bond include, for example, a monomer having an epoxidized unsaturated chain aliphatic hydrocarbon and an ethylenically unsaturated bond. (B1) (hereinafter sometimes referred to as “(b1)”) and a monomer (b2) having an epoxidized structure of an unsaturated alicyclic hydrocarbon and an ethylenically unsaturated bond (hereinafter referred to as “(b2)”) ”).
In the present invention, (b) is preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group. Further, (b) is preferably (b2).

  Specific examples of (b1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl. Ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxy) Methyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxy) Methyl ) Styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6 -Tris (glycidyloxymethyl) styrene, compounds described in JP-A-7-248625, and the like.

  Examples of (b2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclomer A400). Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), and formula (II) And the like.

In the formula (I) and the formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ¹ and X ² each independently represent a single bond, —R ³ —, * —R ³ —O—, * —R ³ —S—, or * —R ³ —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O.

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
As the hydroxyalkyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, Examples include 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O—, * —CH ₂ CH ₂ —O—, and more preferably a single bond, * —CH _2. CH ₂ —O— can be mentioned. Note that * represents a bond with O.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) More preferably, it is a compound represented by Formula (I-1), Formula (I-7), Formula (I-9), or Formula (I-15).

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) More preferably, it is a compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15).

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

Examples of (c) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, as a common name, dicyclopentenyl (meth) Acrylate)), (meth) acrylic acid cycloalkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

  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-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [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-tert-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 (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

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; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 -Diene compounds such as butadiene;
3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3 Oxetanyl group-containing (meth) acrylic esters such as methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane ;
Examples include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuryl group-containing (meth) acrylic acid esters such as tetrahydrofurfuryl methacrylate, and the like.

  Among these, styrene, dicyclopentenyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are copolymerization reactivity and alkali. It is preferable from the viewpoint of solubility.

In the polymer [A1], the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of the structural unit constituting the polymer [A1].
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 resulting coating film, the heat resistance, and the mechanical strength tend to be excellent.

  The polymer [A1] can be obtained by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in literature.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is replaced with nitrogen, thereby heating and heat-retaining with stirring in a deoxygenated atmosphere. The method of doing is illustrated. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as the solvent (E) of the curable resin composition of the present invention.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the same solvent as the solvent (E) described later as the solvent in this polymerization, the solution after the reaction can be used as it is for the preparation of the curable resin composition. The manufacturing process of a thing can be simplified.

In the polymer [A2], the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of all the structural units constituting the polymer [A2].
Structural unit derived from (a); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)
The total 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]. 90 to 99 mol% is more preferable.
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, heat resistance, and mechanical strength of the resulting coating film 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 (meth) acrylic acid / a compound represented by the formula (I-1) (hereinafter abbreviated as “formula (I-1)”. Formula (I-2) And the like are also the same)), (meth) acrylic acid / copolymer of formula (I-2), (meth) acrylic acid / copolymer of formula (I-3), ( (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) Coalescence, (meta Acrylic acid / copolymer of formula (I-13), (meth) acrylic acid / copolymer of formula (I-14), (meth) acrylic acid / copolymer of formula (I-15), (meth ) Acrylic acid / copolymer of formula (II-1), (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), (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 / formula ( I-12), (meth) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / copolymer of formula (II-14), (meth) acrylic acid / formula Copolymer of (II-15), (meth) acrylic acid / copolymer of formula (I-1) / formula (II-1), (meth) acrylic acid / formula (I-2) / formula (II -2) copolymer, (meth) acrylic acid / copolymer of formula (I-3) / formula (II-3), (meth) acrylic acid / formula (I-4) / formula (II-4) ) Copolymer, (meth) acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth) acrylic acid / formula (I-6) / formula (II-6) Copolymer, Copolymer of (meth) acrylic acid / copolymer of formula (I-7) / formula (II-7), Copolymer of (meth) acrylic acid / formula (I-8) / formula (II-8) Coalescence, (meth) acrylic acid / Copolymer of formula (I-9) / formula (II-9), (meth) acrylic acid / copolymer of formula (I-10) / copolymer of formula (II-10), (meth) acrylic acid / formula ( I-11) / copolymer of formula (II-11), (meth) acrylic acid / copolymer of formula (I-12) / copolymer of formula (II-12), (meth) acrylic acid / formula (I- 13) / copolymer of formula (II-13), (meth) acrylic acid / copolymer of formula (I-14) / copolymer of formula (II-14), (meth) acrylic acid / formula (I-15) / Copolymer of formula (II-15), (meth) acrylic acid / copolymer of formula (I-1) / copolymer of formula (I-7), (meth) acrylic acid / formula (I-1) / formula (II-7) copolymer, crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / copolymer of formula (I-3) Coalescence, crotonic acid / formula ( -4), 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 / formula (I-11) ), 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-15), crotonic acid / copolymer of formula (II-1), crotonic acid / copolymer of formula (II-2), crotonic acid / copolymer of formula (II-3) Copolymer, 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 of crotonic acid / formula (II-8), copolymer of crotonic acid / copolymer of formula (II-9), copolymer of crotonic acid / formula (II-10) Polymer, crotonic acid / copolymer of formula (II-11), crotonic acid / copolymer of formula (II-12), crotonic acid / copolymer of formula (II-13), crotonic acid / formula ( II-14), crotonic acid / copolymer of formula (II-15), maleic acid / copolymer of formula (I-1), maleic acid / copolymer of formula (I-2) , Maleic acid / copolymer of formula (I-3), maleic acid / copolymer of formula (I-4), maleic acid / copolymer of formula (I-5), maleic acid / formula (I- 6) copolymer, maleic acid / copolymer of formula (I-7), maleic acid / copolymer of formula (I-8), maleic acid / copolymer of formula (I-9), Maleic acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), maleic acid / copolymer of formula (I-12), maleic acid / formula (I-13) ), Maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15), maleic acid / copolymer of formula (II-1), maleic acid / Copolymer of formula (II-2), maleic acid / copolymer of formula (II-3), maleic acid / copolymer of formula (II-4), maleic acid / copolymer of formula (II-5) Copolymer, maleic acid / copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / copolymer of formula (II-8), maleic acid / formula (II-9) copolymer, maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11), maleic acid / formula ( I-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), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-2), (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 of (meth) acrylic acid / maleic anhydride / copolymer of formula (I-8), (meth) acrylic acid / male Acid anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-10), (meth) acrylic acid / maleic anhydride / formula ( I-11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-13) Polymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-14), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) Acrylic acid / maleic anhydride / copolymer of formula (II-1), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-2), (meth) acrylic acid / maleic anhydride Product / copolymer of formula (II-3), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-4) Polymer, (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 anhydride Product / copolymer of formula (II-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-10), (meth) acrylic acid / maleic anhydride / formula (II- 11), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-13) , (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-14), (meth) Acrylic acid / maleic anhydride / copolymers of formula (II-15) can be mentioned.

  Specific examples of the polymer [A2] include a copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth) ) Acrylate copolymer, (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate copolymer Polymer, copolymer of (meth) acrylic acid / formula (I-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, ( (Meth) acrylic acid / copolymer of formula (I-7) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (I-8) / methyl (meth) acrylate, (meth) acrylic acid / Formula (I-9) / Methyl (meth) acrylate A copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate , (Meth) acrylic acid / copolymer of formula (I-12) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (I-13) / methyl (meth) acrylate, (meth) Acrylic acid / formula (I-14) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-3) ) / Methyl (meta) acrylate Copolymer of (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate , (Meth) acrylic acid / copolymer of formula (II-6) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-7) / methyl (meth) acrylate, (meth) Acrylic acid / formula (II-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-9) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-12) ) / Methyl (meth) acryl Rate copolymer, (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate copolymer Copolymer, copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate , (Meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclopenta Nyl (meth) acrylate copolymer, crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate copolymer, maleic acid / formula (I-1) / dicyclopentanyl (meth) Acrylate copolymer Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Dicyclopentanyl (meth) acrylate copolymer, Crotonic acid / Formula (II-1) / Dicyclopentanyl (meth) acrylate copolymer, Maleic acid / Formula (II-1) / Dicyclopentanyl (Meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II- 1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate copolymer, T) Copolymer of acrylic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate Copolymer, Crotonic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, Copolymer of maleic acid / formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (I-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, croton Copolymer of acid / formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula( II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (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 / formula (I-1) / formula (II-1) / diethyl maleate copolymer, crotonic acid / copolymer of formula (I-1) / diethyl maleate, maleic acid / copolymer of formula (I-1) / diethyl maleate, Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate Polymer, crotonic acid / formula II-1) / diethyl maleate copolymer, maleic acid / formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / maleic Copolymer of diethyl acid, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / diethyl maleate copolymer, (meth) acrylic acid / formula (I-1) / 2-hydroxy Copolymer of ethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / formula (I-1 ) / 2-Hi Roxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I -1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, 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 / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (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] To-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) / methyl (meth) acrylate / bicyclo [2.2.1 ] Hept-2-ene copolymer, (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, corotonic acid / formula (I-1) / N-cyclohexylmaleimide Polymer, maleic acid / formula (I-1) / N-cyclohe Copolymer of silmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (I-1) / methyl (meta ) Copolymer of acrylate / N-cyclohexylmaleimide, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide A copolymer of (meth) acrylic acid / formula (I-1) / styrene, a copolymer of (meth) acrylic acid / formula (II-1) / styrene, ( (Meth) acrylic acid / formula (I-1) / formula (II-1) / styrene copolymer, crotonic acid / formula (I-1) / styrene copolymer, maleic acid / formula (I-1) / Styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Styrene copolymer, Crotonic acid / Formula (II-1) / Styrene copolymer, Maleic acid / Formula (II-1) / Styrene copolymer, (Meth) acrylic acid / Maleic anhydride / Formula (II-1) / styrene copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic Copolymer of acid / formula (II-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene Crotonic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, maleic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / maleic Copolymer of acid anhydride / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene Copolymer, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / formula (II-1) / N-cyclohexylmale Copolymer of imide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / Examples thereof include a methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer.

  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, and further preferably 5,000 to 20,000. Yes, particularly preferably 5,000 to 10,000. When the weight average molecular weight of the polymer (A) is in the above range, the applicability 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 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the obtained coating film tends to be excellent in chemical resistance.

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

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

  The curable resin composition of the present invention is at least one epoxy resin (B) selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter sometimes referred to as “epoxy resin (B)”). including.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether group, and can be produced by reacting phenols, polyhydric alcohols and the like with epichlorohydrin.
Specific examples of the glycidyl ether type epoxy resin include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, and trishydroxyphenylmethane. Type epoxy resin and the like.

The glycidyl ester type epoxy resin is produced by reacting a carbonyl group such as a phthalic acid derivative or a 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.

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

  The glycidyl ether type epoxy resin as described above can be produced by condensing a corresponding phenol and epichlorohydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by methods conventionally known to those skilled in the art. Moreover, you may use a commercial item. As commercially available products of bisphenol A type epoxy resin, for example, jER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation) and the like are used. Can do. As commercial products of bisphenol F type epoxy resin, for example, Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Tohto Kasei Co., Ltd.), or the like can be used. Examples of commercially available phenol novolac epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), and DEN-438 (Dow Chemical). Etc.) can be used. Examples of commercially available o-cresol novolac epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Can be used. As a commercial item of a polyphenol type epoxy resin, for example, Epicoat 1032H60, Epicoat YX-4000 (manufactured by Mitsubishi Chemical Corporation) and the like can be used.

  The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, 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, a method defined in JIS K7236.

The acid value of the epoxy resin (B) is usually less than 30 mg-KOH / g, and more preferably 10 mg-KOH / g or less.
Moreover, the weight average molecular weight of an epoxy resin (B) becomes like this. Preferably it is 300-10,000, More preferably, it is 400-6,000, More preferably, it is 500-4,800.

The content of the epoxy resin (B) is preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the total content of the polymer (A) and the epoxy resin (B). When the content of the polymer (A) is in the above range, the resulting coating film tends to have excellent adhesion to the substrate.
The total content of the polymer (A) and the epoxy resin (B) is preferably 50 to 98% by mass, more preferably 55 to 85% by mass, based on the solid content of the curable resin composition. . When the total content is in the above range, the resulting coating film tends to be excellent in chemical resistance. Here, solid content of curable resin composition means the quantity remove | excluding the solvent (E) from 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 acid anhydride and a polyvalent carboxylic acid (hereinafter sometimes referred to as “compound (C)”). The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The compound (C) preferably has a molecular weight of 3000 or less, and more preferably 1000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecyl succinic anhydride, 2- (2 octa- 3-enyl) succinic anhydride, 2- (2,4,6-trimethylnon-3-enyl) succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Chain polycarboxylic acid anhydrides such as
3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride , Norbornene dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2 2.2.1] hept-5-ene-2,3-dicarboxylic anhydride (hymic anhydride), methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, cyclo An alicyclic polycarboxylic acid anhydride such as pentanetetracarboxylic dianhydride;
Phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3'4,4'-diphenylsulfonetetra Carboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), glycerin tris (anhydro trimellitate), glycerin bis (anhydro trimellitate) monoacetate, 1,3,3a, 4,5,9b -Aromatic polycarboxylic acid anhydrides such as hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione;
ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by ADEKA Corporation), Rikacid-HH, same-TH, same-MH, same MH-700 (new Nippon Rika Co., Ltd.), Epikinia 126, same Commercial products such as YH-306 and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and chain polyvalent carboxylic acid that leads to chain polyvalent carboxylic acid anhydride. carboxylic acid;
Cycloaliphatic polycarboxylic acids such as cyclohexanedicarboxylic acid and polyvalent carboxylic acids leading to alicyclic polycarboxylic anhydrides;
And aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and polyvalent carboxylic acids that lead to aromatic polyvalent carboxylic acid anhydrides.

These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids may be used alone or in combination of two or more.
Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable because of excellent heat resistance of the coating film, and transparency in the visible light region is particularly difficult to decrease. An acid anhydride is more preferable.

  Content of the compound (C) in the curable resin composition of this invention becomes like this. Preferably it is 1-30 mass% with respect to 100 mass parts of polymers (A), More preferably, it is 3-20 mass%. When the content of the compound (C) is within the above range, the coating film has excellent heat resistance and adhesion, and even when a coating film is formed on a substrate on which minute foreign substances exist, the fine foreign substances are concentrically formed. There is a tendency that uneven spreading is less likely to occur, and the chemical resistance of the coating film also tends to be excellent.

  The curable resin composition of the present invention preferably contains an antioxidant (D). Examples of the antioxidant (D) include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 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′-me Renbis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', "-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di- Examples thereof include tert-butyl-4-methylphenol, etc. Commercial products such as IRGANOX 3114 (manufactured by Ciba Japan) may be used.

  The content of the antioxidant (D) is 0.1 part by mass or more and 5 parts by mass or less, and preferably 0.5 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polymer (A). When the content of the antioxidant (D) is within the above range, the resulting coating film tends to be excellent in heat resistance and pencil hardness. When content of antioxidant (D) exceeds the said range, there exists a possibility that the pencil hardness of a coating film may fall.

  The curable resin composition of the present invention has a compound (F) (hereinafter, referred to as “(meth) acryloyl group”) having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter sometimes referred to as “(meth) acryloyl group”). It is preferable to contain (sometimes referred to as “(meth) acrylic compound (F)”). The curable resin composition of the present invention tends to improve the hardness and chemical resistance of the coating film by including the (meth) acrylic compound (F).

  Examples of the (meth) acrylic compound (F) having one (meth) acryloyl group include the same compounds as those mentioned as the above (a), (b) and (c), and among them, (meth) acrylic acid Esters are preferred.

  Examples of the (meth) acrylic compound (F) having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol diene. (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol Ruji (meth) acrylate, 3-methyl-pentanediol di (meth) acrylate.

Examples of the (meth) acrylic compound (F) having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane 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, Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, Tripentaerythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone Dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta ( (Meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Products, caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydrides, etc. .
As the (meth) acrylic compound (F), a (meth) acrylic compound (F) having three or more (meth) acryloyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

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

The curable resin composition of the present invention preferably contains a solvent (E).
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. Can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents 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, diethylene 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-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, ethyleneglycol monomethyl ether acetate, ethyleneglycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

  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, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and a mixed solvent containing these are preferable.

  Content of the solvent (E) in curable resin composition becomes like this. Preferably it is 60-95 mass% with respect to curable resin composition, More preferably, it is 70-95 mass%. In other words, the solid content of the curable resin composition is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. If the content of the solvent (E) is in the above range, the flatness of the film coated with the curable resin composition tends to be high.

  The curable resin composition of the present invention may contain a surfactant (G). Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning 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 Japan GK) Manufactured) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  Surfactant (G) is 0.001 mass% or more and 0.2 mass% or less with respect to curable resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably It is 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in this range, the flatness of the coating film can be improved.

  In the curable resin composition of the present invention, additives such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, curing accelerators, etc., are included as necessary. May be contained.

Examples of the filler include glass, silica, and alumina.
Examples of other polymer compounds include thermosetting resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

Specific examples of the thermal radical generator include 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.
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 vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycol. Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3 Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc. Can be mentioned.
Examples of the curing accelerator include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, 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) imi Dazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl- Examples include 4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and the like.

  The curable resin composition of the present invention contains substantially no photopolymerization initiator. That is, in the curable resin composition of the present invention, the content of the photopolymerization initiator with respect to the entire composition is, for example, less than 1% by mass, and preferably less than 0.5% by mass. Examples of the photopolymerization initiator include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds.

  Further, 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 with respect to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

  Moreover, the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and the transmittance is measured when the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. Is preferably 70% or more, and more preferably 80% or more.

  When the curable resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a coating film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured by. Thereby, the coating film excellent in transparency in the visible light region can be provided.

  The curable resin composition of the present invention comprises a copolymer (A), an epoxy resin (B) and a compound (C), a (meth) acrylic compound (F), a solvent (E) and other components as necessary. It can be produced by stirring and mixing by a conventionally known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

A coating film can be produced by applying the curable resin composition of the present invention on a substrate and curing it by heat.
Examples of the substrate include glass, metal, and plastic, and a color filter, various insulating films or conductive films, a drive circuit, and the like may be formed on the substrate.
It is preferable to apply the curable resin composition of the present invention on the substrate using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.

After application, it is preferable to remove volatile components such as a solvent by vacuum drying or pre-baking.
The coating film from which the volatile components have been removed is preferably subjected to post baking at 150 to 240 ° C. for 10 to 120 minutes to form a coating film.

  The coating film thus obtained is useful as an overcoat used for, for example, a liquid crystal display device, an organic EL display device or electronic paper. Moreover, it can also be used for a display device member such as a touch panel. ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to manufacture the display apparatus provided with the high quality coating film with a high yield.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring. Subsequently, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A mixture was prepared by dissolving 360 parts by mass of a mixture of the compounds to be prepared (molar ratio = 50: 50) in 190 parts by mass of diethylene glycol ethyl methyl ether. The obtained solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.
On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of diethylene glycol ethyl methyl ether was added to a flask over another 5 hours using another dropping pump. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and the solid content was 42.6% by mass and the acid value was 60 mg-KOH / g (solid content conversion). A solution of the polymer (resin Aa) was obtained. 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
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow 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 and stirred. While heating to 70 ° C. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) (Mix ratio of compound: 50:50) 240 parts are dissolved in 140 parts of 3-methoxybutylacetate to prepare a solution, and this solution is added over 70 hours using a dropping funnel over 70 hours. The solution was dropped into a flask kept at a temperature of ° C.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The solid content was 32.6% and the acid value was 110 mg-KOH / g (solid content conversion). A solution of coalescence (resin Ab) was obtained. 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 number average molecular weight (Mn) of the obtained resins Aa and Ab were measured using the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

(Examples 1-7 and Comparative Examples 1-2)
The composition of Table 1 was mixed to obtain a curable resin composition.

エポキシ樹脂（Ｂ）；ビスフェノールＡ型エポキシ樹脂（ｊＥＲ１５７Ｓ７０；三菱化学（株）製）
化合物（Ｃ１）；１，２，３，６−テトラヒドロフタル酸無水物（リカシッドＴＨ；新日本理化（株）製；下記式で表される化合物）

化合物（Ｃ２）；ヘキサヒドロフタル酸無水物（リカシッドＨＨ；新日本理化（株）製；下記式で表される化合物）

化合物（Ｃ３）；４−メチルヘキサヒドロフタル酸無水物（リカシッドＭＨ；新日本理化（株）製；下記式で表される化合物

化合物（Ｃ４）；５−ノルボルネン−２，３−ジカルボン酸無水物（和光純薬工業（株）製；下記式で表される化合物

化合物（Ｃ５）；トリメリット酸無水物（関東化学（株）製）
酸化防止剤（Ｄ）；１，３，５−トリス（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン（ＩＲＧＡＮＯＸ３１１４；チバ・ジャパン株式会社製）
（メタ）アクリル化合物（Ｆ）；ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ ＤＰＨＡ；日本化薬（株）製）
界面活性剤（Ｇ）；ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製 ＳＨ８４００）
重合開始剤（Ｈ１）；Ｃｂ；２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール（Ｂ−ＣＩＭ；保土谷化学（株）製）
重合開始助剤（Ｈ２）；Ｃ２a；２−（２−ナフトイルメチレン）−３−メチルベンゾチアゾリン
重合開始助剤（Ｈ３）；ペンタエリスリトールテトラキスプロピオネート（ＰＥＭＰ；ＳＣ有機化学（株）製）

Epoxy resin (B); bisphenol A type epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Corporation)
Compound (C1); 1,2,3,6-tetrahydrophthalic anhydride (Licacid TH; manufactured by Shin Nippon Rika Co., Ltd .; compound represented by the following formula)

Compound (C2); hexahydrophthalic anhydride (Licacid HH; manufactured by Shin Nippon Rika Co., Ltd .; compound represented by the following formula)

Compound (C3); 4-methylhexahydrophthalic anhydride (Licacid MH; manufactured by Shin Nippon Rika Co., Ltd.); a compound represented by the following formula

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

Compound (C5); trimellitic anhydride (manufactured by Kanto Chemical Co., Inc.)
Antioxidant (D); 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trion (IRGANOX3114; manufactured by Ciba Japan Co., Ltd.)
(Meth) acrylic compound (F); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Surfactant (G); polyether-modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.)
Polymerization initiator (H1); Cb; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; Hodogaya Chemical ( Made by)
Polymerization initiation assistant (H2); C2a; 2- (2-naphthoylmethylene) -3-methylbenzothiazoline polymerization initiation assistant (H3); pentaerythritol tetrakispropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

<Permeability of composition>
Each of the obtained curable resin compositions was averaged at 400 to 700 nm using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The transmittance (%) was measured. The results are shown in Table 1.

<The coating-film preparation methods of Examples 1-7 and Comparative Example 1>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and isopropanol and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 90 ° C. for 10 minutes in a clean oven. Thereafter, the film was obtained by heating at 230 ° C. for 40 minutes.
<The coating-film preparation method of the 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. On this glass substrate, the curable resin composition is exposed at an exposure amount (405 nm) of 200 mJ / cm2, spin-coated so that the film thickness after development, water washing and post-baking becomes 2.0 μm, and then Pre-baked at 90 ° C. for 3 minutes in a clean oven. After cooling, the substrate coated with this curable resin composition was exposed to 100 mJ / cm ² (405 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source; ultrahigh pressure mercury lamp). (Reference). In addition, the irradiation to the curable resin composition at this time was performed by passing the light emitted from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.) and cutting light of 400 nm or less. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for 100 seconds at 25 ° C. for development, washed with water, A film was obtained by heating at 0 ° C. for 20 minutes.

<Average transmittance of coating film>
The transmittance | permeability (%) in 400 nm and the average transmittance (%) in 400-700 nm were measured for the obtained coating film using the microspectrophotometer (OSP-SP200; OLYMPUS company make). The results are shown in Table 1.

<Heat resistance>
The obtained coating film was heat-treated at 240 ° C. for 4 hours, the transmittance at 400 nm before and after heating was measured, and the change in transmittance (%) was determined according to the following formula. In any case, the closer to 100%, the smaller the coloration or decoloration of the coating film before and after heating. The results are shown in Table 1.

  Change in transmittance (%); (transmittance after heating (%) / transmittance before heating (%)) × 100

<Adhesion>
The same operation as described above was performed except that the glass substrate was replaced with a glass substrate with ITO, and a coating film was produced on the 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 Seisakusho Co., Ltd.) for 2 hours, then JIS K-5400-1990 8 .5.3 Adhesiveness The adhesion of the coating film to the glass substrate with ITO was evaluated by a cross-cut tape method. Table 1 shows the number of grids remaining on the substrate out of 100 grids as adhesion (pieces).

As shown in Table 1, it was confirmed that the coating film obtained from the curable resin composition of the present invention containing the compound (C) was excellent in adhesion to the substrate even in a high temperature and high humidity environment.
By using a coating film formed from such a curable resin composition, a display device having excellent durability can be produced.

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

Claims (5)

Curable resin composition containing (A), (B) and (C) (however, a compound having a basic skeleton structure described by the following formula (1) and / or a compound having a basic skeleton structure described by the following formula (2) Is not included.)
(A) Epoxy unsaturated alicyclic hydrocarbon having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, oxiranyl group and ethylenically unsaturated bond A copolymer containing a structural unit derived from a monomer having a structured structure and an ethylenically unsaturated bond (B) at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin ( C) At least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids

  The curable resin composition according to claim 1, further comprising a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.   Furthermore, the curable resin composition of Claim 1 or 2 containing antioxidant. Coating film formed by the curable resin composition of any of claims 1-3.   A display device comprising the coating film according to claim 4.