JP6119167B2 - 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 compositions, the heat resistance of a coating film formed by applying the curable resin composition to a substrate may not always be sufficiently satisfied.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、互いに独立に、式（ａ）で表される基又は式（ｂ）で表される基を表す。］

［式（ａ）及び式（ｂ）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。］
［２］ 式（１）で表される化合物の含有量が、樹脂１００質量部に対して、５質量部以上６０質量部以下である［１］記載の硬化性樹脂組成物。
［３］ さらに、酸化防止剤を含む［１］又は［２］記載の硬化性樹脂組成物。
［４］［１］〜［３］のいずれかに記載の硬化性樹脂組成物により形成される塗膜。
［５］［４］記載の塗膜を含む表示装置。 The present invention provides the following [1] to [5].
[1] 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 acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond And a curable resin composition containing a compound represented by formula (1).

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

[In Formula (a) and Formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
[2] The curable resin composition according to [1], wherein the content of the compound represented by the formula (1) is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the resin.
[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 curable resin composition of this invention, the coating film excellent in heat resistance can be manufactured.

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

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、互いに独立に、式（ａ）で表される基又は式（ｂ）で表される基を表す。］

［式（ａ）及び式（ｂ）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。］ The curable resin composition of the present invention includes a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated group. A resin containing a structural unit derived from a monomer having a saturated bond (hereinafter sometimes referred to as “resin (A)”), and a compound represented by formula (1) (hereinafter referred to as “compound (1)”) In some cases).

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

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

Furthermore, it is preferable that the curable resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of antioxidant (D), a solvent (E), and surfactant (G).

Further, the curable resin composition of the present invention has at least one epoxy resin 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)”). , At least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids (hereinafter sometimes referred to as “polyvalent carboxylic acid (C)”), a group consisting of acryloyl group and methacryloyl group. A compound having at least one selected group (hereinafter, sometimes referred to as “(meth) acryloyl group”) (hereinafter, sometimes referred to as “(meth) acrylic compound (F)”), and an imidazole compound (hereinafter, referred to as “(meth) acryloyl group”). It may include at least one selected from the group consisting of “sometimes referred to as“ imidazole compound (H) ””.
The curable resin composition of the present invention contains substantially no polymerization initiator.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、互いに独立に、式（ａ）で表される基又は式（ｂ）で表される基を表す。］

［式（ａ）及び式（ｂ）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。］ <Compound (1)>
When the curable resin composition of this invention contains a compound (1), the coating film obtained from this curable resin composition will be excellent in heat resistance.

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

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

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and an octyl group.
R ⁴ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom or a methyl group.

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

Examples of compound (1) include compounds represented by formula (1-1) to formula (1-7). Preferably, it is a compound represented by Formula (1-1)-Formula (1-4).

<Resin (A)>
The resin (A) includes a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a 0 )”), 4 and a structural unit derived from a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b 0 )”). The resin (A) further comprises a structural unit derived from a monomer that is different from (a 0 ) and (b 0 ) and copolymerizable therewith (hereinafter sometimes referred to as “(c 0 )”). You may have.
Examples of the resin (A) include the following resin [K1] and resin [K2].
Resin [K1]: Copolymer of (a 0 ) and (b 0 );
Resin [K2]: a copolymer of (a 0 ), (b 0 ), and (c 0 ).

<Resin (A)>
The resin (A) is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and has 2 to 4 carbon atoms. And a structural unit derived from a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”). The resin (A) further has a structural unit derived from a monomer that is different from (a) and (b) and copolymerizable therewith (hereinafter sometimes referred to as “(c)”). May be.
Examples of the resin (A) include the following resin [K1] and resin [K2].
Resin [K1]: Copolymer of (a) and (b);
Resin [K2]: a copolymer of (a), (b) and (c).

Specific examples of (a 0 ) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene 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 or a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, (meth) acrylic acid and maleic anhydride are preferred, and (meth) acrylic acid is more preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

(B 0 ) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B 0 ) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b 0 ) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Is mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), 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 (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by the formula (II).

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

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.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups 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 ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond and * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), and Formula (I-11) to Formula (I-15) A compound represented by any one of formula (I-1), formula (I-7), formula (I-9) and formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15) A compound represented by any one of formulas (II-1), (II-7), (II-9) and (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or as a mixture in any ratio. When used as a mixture, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(B 0 ) is preferably (b 1 ) from the viewpoint that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the curable resin composition is excellent.

Examples of (c 0 ) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1. 0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. Also referred to as “tricyclodecyl (meth) acrylate”) Sometimes) Licyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as “dicyclopentenyl (meth) acrylate”), dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
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 [2.2 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, etc. Bicyclounsaturated 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 and N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoints of copolymerization reactivity and heat resistance. .

In the resin [K1], the ratio of the structural units derived from the respective monomers is the resin [K1].
For all structural units that make up
Structural unit derived from (a 0 ); 5 to 60 mol%
Structural unit derived from (b 0 ); 40 to 95 mol%
Is preferred,
Structural unit derived from (a 0 ); 10-50 mol%
Structural unit derived from (b 0 ); 50 to 90 mol%
Is more preferable.
When the ratio of the structural units constituting the resin [K1] is within 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 resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

Specifically, a predetermined amount of (a 0 ) and (b 0 ), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated by, for example, replacing oxygen with nitrogen and stirring. However, the method of heating and heat-retaining is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used, and examples of the solvent for the curable resin composition include a solvent (E) described later.

  In addition, the obtained resin may use the solution after the reaction as it is, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation. May be used. In particular, by using the solvent (E) described later as a solvent during the polymerization, the solution after the reaction can be used as it is for the production of the curable resin composition, so that the process for producing the curable resin composition Can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a 0 ); 2 to 40 mol%
Structural unit derived from (b 0 ); 2-95 mol%
Structural unit derived from (c 0 ); 1 to 65 mol%
It is preferable that
Structural unit derived from (a 0 ); 5-35 mol%
Structural unit derived from (b 0 ); 5 to 80 mol%
Structural unit derived from (c 0 ); 1-60 mol%
It is more preferable that
The total amount of the structural unit derived from (a 0 ) and the structural unit derived from (b 0 ) is 70 to 99 mol% with respect to the total number of moles of all structural units constituting the resin [K2]. Is preferable, and 90 to 99 mol% is more preferable.
When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable resin composition, the chemical resistance, heat resistance, and mechanical strength of the resulting coating film tend to be excellent.
Resin [K2] can be manufactured by the same method as resin [K1].

  Specific examples of the resin [K1] include (meth) acrylic acid / a compound represented by formula (I-1) (hereinafter sometimes abbreviated as “formula (I-1)”. Formula (I-2) Etc., etc.), (meth) acrylic acid / copolymer of formula (I-2), (meth) acrylic acid / copolymer of formula (I-3), (meta ) 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) , (Meta) Copolymer of crylic acid / formula (I-13), copolymer of (meth) acrylic acid / formula (I-14), copolymer of (meth) acrylic acid / 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), copolymer of (meth) acrylic acid / 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), copolymer of (meth) acrylic acid / formula (I-6) / formula (II-6) Polymer, copolymer of (meth) acrylic acid / formula (I-7) / formula (II-7), copolymer of (meth) acrylic acid / formula (I-8) / formula (II-8) , (Meth) acrylic acid / formula (I-9) / copolymer of 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), copolymer of (meth) acrylic acid / formula (I-1) / formula (I-7), (meth) acrylic acid / formula (I-1) / formula ( II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / copolymer of formula (I-3) Crotonic acid / formula (I 4) copolymer, crotonic acid / copolymer of formula (I-5), crotonic acid / copolymer of formula (I-6), crotonic acid / copolymer of formula (I-7), croton Acid / copolymer of formula (I-8), crotonic acid / copolymer of formula (I-9), crotonic acid / copolymer of formula (I-10), crotonic acid / copolymer of formula (I-11) Copolymer, 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), copolymer of crotonic acid / formula (II-1), copolymer of crotonic acid / formula (II-2), copolymer of crotonic acid / formula (II-3) Polymer, crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / (II-7) copolymer, crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / copolymer of formula (II-10) 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 / copolymer of formula (I-6) ), Maleic acid / copolymer of formula (I-7), maleic acid / copolymer of formula (I-8), maleic acid / copolymer of formula (I-9), Rain 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 / formula (I-5) copolymer, (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 / formula (I -11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-13) Copolymer, (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 / Copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-4) Copolymer, (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 / 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) a Copolymers of acrylic acid / maleic anhydride / formula (II-15) can be mentioned.

  Specific examples of the resin [K2] include a copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth). Copolymer of acrylate copolymer, (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate (Meth) acrylic acid / formula (I-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate copolymer, ) Acrylic acid / Formula (I-7) / Methyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-8) / Methyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-9) / Methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, 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 (meth) acrylate Copolymer, 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 / formula (II-6) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate copolymer, (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) acrylate Copolymer, (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate copolymer Polymer, Copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclo Pentanyl (meth) acrylate copolymer, crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate copolymer, maleic acid / formula (I-1) / dicyclopentanyl (meta ) Acrylate copolymer, Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / di Copolymer of cyclopentanyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, 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, ) Acrylic acid / Formula (II-1) / Phenyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-1) / Formula (II-1) / Phenyl (meth) acrylate copolymer , Crotonic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, maleic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride Product / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, crotonic acid / Copolymer of formula (II-1) / phenyl (meth) acrylate, maleic acid / copolymer of formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I I-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 ( I-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-Hide Copolymer of xylethyl (meth) acrylate, (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, 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 / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meta ) Acrylic acid / maleic anhydride / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meta ) Acrylate / bicyclo [2.2.1] hept-2-ene copolymer, crotonic acid / formula (II-1) / bicyclo [2.2.1] hept 2-ene copolymer, maleic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / maleic anhydride / formula ( II-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / bicyclo [2.2.1] Copolymer of hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, corotate of crotonic acid / formula (I-1) / N-cyclohexylmaleimide Compound, maleic acid / formula (I-1) / N-cyclohex Rumaleimide copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (I-1) / methyl (meth) 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 Copolymer, (meth) acrylic acid / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (II-1) / styrene copolymer, A) 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 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 acid Copolymer of anhydride / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene A copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / formula (II-1) / N-cyclohexylmale / Styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / formula (II-1) / Examples thereof include a methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer.

The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 20,000. Particularly preferred is 5,000 to 10,000. When the weight average molecular weight of the resin (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 resin (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 resin (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, particularly preferably 50 mg-KOH / g. It is 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 resin (A) is within the above range, the resulting coating film tends to have excellent adhesion to the substrate.

  Content of resin (A) becomes like this. Preferably it is 30-90 mass% with respect to solid content of the curable resin composition of this invention, More preferably, it is 40-80 mass%. When the content of the resin (A) is within the above range, the obtained coating film tends to be excellent in adhesion to the substrate and chemical resistance. Here, solid content of curable resin composition means the quantity remove | excluding the solvent (E) from the total amount of the curable resin composition of this invention.

<Epoxy resin (B)>
The epoxy resin (B) is not particularly limited except that it has a structure different from that of the resin (A), but at least one selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins is preferable.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized 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 an epoxy resin having a glycidyl ester structure, and is synthesized 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 p-oxybenzoic acid, m-oxybenzoic acid, and a glycidyl ester type epoxy resin derived from an aromatic carboxylic acid such as 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 synthesized 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. For example, as commercial products of bisphenol A type epoxy resin, 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 a commercially available product of bisphenol F type epoxy resin, Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Toto Kasei Co., Ltd.) and the like can be used. Commercially available phenol novolac epoxy resins include Epicoat 152, Epicoat 154 (Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (Nippon Kayaku Co., Ltd.), DEN-438 (Dow Chemical Co. ) Etc. can be used. As commercial products of o-cresol novolac type epoxy resin, EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), etc. should be used. Can do. As a commercial product of a polyphenol type epoxy resin, 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, more preferably 5 to 40% by mass with respect to the total content of the resin (A) and the epoxy resin (B). When content of resin (A) exists in the said range, the coating film obtained tends to be excellent in adhesiveness with a board | substrate.
The total content of the resin (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 of the present invention. It is. When the total content is in the above range, the resulting coating film tends to be excellent in chemical resistance.

<Polyvalent carboxylic acid (C)>
The polyvalent carboxylic acid (C) is at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. 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 polyvalent carboxylic acid (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 2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, dicyclopentanetetracarboxylic acid diacid Alicyclic polycarboxylic acid anhydrides such as anhydrides;
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 such as polyvalent carboxylic acid that leads to chain polycarboxylic acid anhydride. acid;
Cycloaliphatic polycarboxylic acids such as cyclohexanedicarboxylic acid, 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.

  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.

  The content of the polyvalent carboxylic acid (C) is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to 100 parts by mass of the resin (A). When the content of the polyvalent carboxylic acid (C) is within the above range, the heat resistance and adhesion of the coating film are excellent.

<Antioxidant (D)>
Examples of the antioxidant (D) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among these, a phenolic antioxidant is preferable in that the coating film is less colored.

Examples of phenolic antioxidants 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, 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′-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methyl) Ruphenol), 2,2′-thiobis (6-tert-butyl-4-methylphenol), 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 ', a "- (Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert- Butyl-4-methylphenol, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3 2] dioxaphosphepin and the like.
A commercial item may be used as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all are manufactured by BASF).

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3 -Lauryl thiopropionate) and the like. A commercially available product may be used as the sulfur-based antioxidant. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1, Examples include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. A commercially available product may be used as the phosphorus-based antioxidant. Examples of commercially available phosphorus antioxidants include Irgaphos (registered trademark) 168, 12, and 38 (all manufactured by BASF), Adeka Stub 329K, Adeka Stub PEP36 (all manufactured by ADEKA), and the like.

  Examples of amine-based antioxidants include N, N′-di-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, and N, N′-dicyclohexyl-p-phenylene. Examples include diamine, N, N′-diphenyl-p-phenylenediamine, and N, N′-bis (2-naphthyl) -p-phenylenediamine. A commercially available product may be used as the amine-based antioxidant. Examples of commercially available amine-based antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  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 resin (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.

〔式（１）中、Ｒ^１１は、炭素数１〜２０のアルキル基、フェニル基、ベンジル基又は炭素数２〜５のシアノアルキル基を表す。
Ｒ^１２〜Ｒ^１４は、互いに独立に、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、フェニル基、ニトロ基又は炭素数１〜２０のアシル基を表し、該アルキル基及び該フェニル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。〕 <Imidazole compound (H)>
The imidazole compound (H) is not particularly limited as long as it is a compound having an imidazole skeleton. For example, a compound known as an epoxy curing agent can be used. Among these, a compound represented by the formula (2) is preferable.

Wherein ^{(1), R 11} represents an alkyl group, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms having 1 to 20 carbon atoms.
R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group The hydrogen atom contained in may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and heptadecyl group. And an undecyl group.
Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristolyl group, stearoyl group and the like.

  Examples of the imidazole compound (H) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole. 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxy Methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxy Phenyl) imidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2- Examples include ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and the like. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

  The content of the imidazole compound (H) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 1.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin (A). When the content of the imidazole compound (H) is in the above range, the resulting coating film tends to be excellent in transparency.

<(Meth) acrylic compound (F)>
The (meth) acrylic compound (F) is a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

  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, Reaction product of 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, cap Lolactone-modified 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, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction product, caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride And the like.
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 resin (A). When the content of the (meth) acrylic compound (F) is in the above range, the chemical resistance and mechanical strength of the resulting coating film tend to be good.

<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 and dimethyl sulfoxide. It can be used by selecting from among them.

  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.

  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 a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of the curable resin composition of this invention, More preferably, it is 70-95 mass%. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40% by mass, 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.

<Surfactant (G)>
Examples of the surfactant (G) include silicone surfactants, fluorine surfactants, silicone surfactants 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 the total amount of the curable resin composition of this invention, Preferably it is 0.002 mass% or more and 0.1 mass%. Below, more preferably 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.

<Other ingredients>
Addition of a filler, other polymer compound, a thermal radical generator, a UV absorber, a chain transfer agent, an adhesion promoter, a thermal acid generator, etc., to the curable resin composition of the present invention, as necessary. An agent 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 thermal acid generator include thermal acid generators described in JP 2010-152335 A.

  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 relative to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass, more preferably less than 0.1% by mass. It is. 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.

<Method for producing curable resin composition of the present invention>
The curable resin composition of the present invention comprises a compound (1) and a resin (A), and an epoxy resin (B), a polyvalent carboxylic acid (C), an antioxidant (D), ( It can be produced by mixing the (meth) acrylic compound (F), the solvent (E) and other components by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<The manufacturing method of the coating film of this invention>
The coating film formed from the curable resin composition of the present invention 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, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed over the substrate.
Coating on the substrate is preferably performed 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 a protective film or overcoat for color filters and touch panels used for liquid crystal display devices, organic EL display devices and electronic paper, for example. Thereby, it is possible to manufacture a display device having a 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.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をジエチレングリコールエチルメチルエーテル２４０部に溶解させた溶液を、別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤溶液の滴下が終了した後、７０℃で４時間保持し、その後室温まで冷却して、固形分４２．３％の共重合体（樹脂Ａａ）の溶液を得た。得られた樹脂Ａａの重量平均分子量（Ｍｗ）は８０００、分子量分布（Ｍｗ／Ｍｎ）は１．９１、固形分換算の酸価は６０ｍｇ−ＫＯＨ／ｇであった。下記の構造単位を有する。

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 of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring. Then 40 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} A solution having 360 parts dissolved in 190 parts of diethylene glycol ethyl methyl ether was prepared, and this solution was dropped into a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was placed in a flask over another 5 hours using another dropping pump. It was dripped. 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 to obtain a copolymer (resin Aa) solution having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the molecular weight distribution (Mw / Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH / g. It has the following structural units.

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 [5.2.12.02.6] decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1) Mixture of compounds in a molar ratio of 50:50) 240 parts are dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution is added to a 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm. On the other hand, a solution obtained by dissolving 30 parts of 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 solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin Ab) solution having a solid content of 32.6%. The obtained resin Ab had a weight average molecular weight Mw of 13,400, a molecular weight distribution (Mw / Mn) of 2.50, and an acid value in terms of solid content of 110 mg-KOH / g.

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.

バインダー樹脂（Ａ）；Ａａ〜Ａｂ；樹脂Ａａ〜Ａｂ
化合物 1 ；モノアリルジグリシジルイソシアヌル酸（ＭＡ−ＤＧＩＣ；四国化成工業（株）製）
化合物 ２ ；ジアリルモノグリシジルイソシアヌル酸（ＤＡ−ＭＧＩＣ；四国化成工業（株）製）
化合物 ３ ；トリアリルイソシアヌル酸（ＴＡＩＣ；日本化成（株）製）
化合物 ４ ；トリメタリルイソシアヌル酸（ＴＭＡＩＣ；日本化成（株）製）
エポキシ樹脂（Ｂ）；Ｂａ；ビスフェノールＡ型エポキシ樹脂（ｊＥＲ１５７Ｓ７０；三菱化学（株）製
多価カルボン酸（Ｃ）；Ｃａ；ブタンテトラカルボン酸（リカシッドＢＴ−Ｗ；新日本理化株式会社製）
多価カルボン酸（Ｃ）；Ｃb；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（ＩＲＧＡＮＯＸ（登録商標）３１１４；ＢＡＳＦ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）
イミダゾール化合物（Ｈ）；Ｈ；１−ベンジル−２−フェニルイミダゾール（キュアゾール１Ｂ２ＰＺ；四国化成工業（株）製）
界面活性剤（Ｇ）；ポリエーテル変性シリコーンオイル（トーレシリコーンＳＨ８４００；東レ・ダウコーニング（株）製）
溶剤（Ｅ）は、硬化性樹脂組成物の固形分量が表１の「固形分量（％）」となるように混合し、溶剤（Ｅ）中の溶剤成分の値は、溶剤（Ｅ）中の質量比を表す。 Examples 1-8 and Comparative Example 1
<Preparation of curable resin composition>
Each component shown in Table 1 was mixed in the ratio shown in Table 1 to obtain a curable resin composition.
[Table 1]

Binder resin (A); Aa to Ab; Resin Aa to Ab
Compound 1: Monoallyl diglycidyl isocyanuric acid (MA-DGIC; manufactured by Shikoku Chemicals Co., Ltd.)
Compound 2; diallyl monoglycidyl isocyanuric acid (DA-MGIC; manufactured by Shikoku Chemicals Co., Ltd.)
Compound 3; triallyl isocyanuric acid (TAIC; manufactured by Nippon Kasei Co., Ltd.)
Compound 4; trimethallyl isocyanuric acid (TMAIC; manufactured by Nippon Kasei Co., Ltd.)
Epoxy resin (B); Ba; bisphenol A type epoxy resin (jER157S70; polyvalent carboxylic acid (C) manufactured by Mitsubishi Chemical Corporation; Ca; butanetetracarboxylic acid (Licacid BT-W; manufactured by Shin Nippon Rika Co., Ltd.)
Polyvalent carboxylic acid (C); Cb; 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) ) -Trione (IRGANOX (registered trademark) 3114; manufactured by BASF)
(Meth) acrylic compound (F); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Imidazole compound (H); H; 1-benzyl-2-phenylimidazole (Curazole 1B2PZ; manufactured by Shikoku Chemicals Co., Ltd.)
Surfactant (G); polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
The solvent (E) is mixed so that the solid content of the curable resin composition is “solid content (%)” in Table 1, and the value of the solvent component in the solvent (E) is the same as that in the solvent (E). Represents the mass ratio.

<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 3.

<Preparation of coating film>
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. Then, it heated at 230 degreeC for 40 minutes and obtained the coating film.

<Film thickness measurement>
In the examples, the film thickness of the coating film was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.) with a measurement width of 500 μm and a measurement speed of 10 seconds.

<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 3.

<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 3.

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

<Evaluation of flatness; production of evaluation substrate>
Each component shown in Table 2 was mixed in the ratio shown in Table 2 to obtain a colored photosensitive resin composition.

２インチ角のガラス基板（イーグルＸＧ；コーニング社製）を、中性洗剤、水及びイソプロパノールで順次洗浄してから乾燥させた。このガラス基板上に、着色感光性樹脂組成物を、ポストベーク後の膜厚が１．４μｍになるようにスピンコートした。次に、クリーンオーブン中、９０℃で３分間プリベークして着色組成物層を形成した。放冷後、基板上の着色組成物層と石英ガラス製フォトマスクとの間隔を１００μｍとし、露光機（ＴＭＥ−１５０ＲＳＫ；トプコン（株）製、光源；超高圧水銀灯）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ^２の露光量（３６５ｎｍ基準）で光照射した。なお、この光照射は、超高圧水銀灯からの放射光を、光学フィルタ（ＵＶ−３５；旭テクノグラス（株）製）を通過させて行った。また、フォトマスクとしては、線幅３０μｍのラインアンドスペースパターンを形成するためのフォトマスクを用いた。光照射後、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％を含む水系現像液に上記塗膜を２３℃で８０秒間浸漬して現像し、水洗後、オーブン中、２２０℃で２０分間ポストベークを行い、線幅３０μｍのラインアンドスペースの着色パターンが形成された評価用基板を作成した。
形成された着色パターンの膜厚を測定したところ、１．４μｍであることを確認した。 [Table 2]

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 colored photosensitive resin composition was spin-coated so that the film thickness after post-baking was 1.4 μm. Next, pre-baking was performed at 90 ° C. for 3 minutes in a clean oven to form a colored composition layer. After allowing to cool, the distance between the colored composition layer on the substrate and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used in an atmospheric environment. , And was irradiated with light at an exposure amount of 100 mJ / cm ² (based on 365 nm). In addition, this light irradiation performed the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-35; Asahi Techno Glass Co., Ltd. product). As the photomask, a photomask for forming a line and space pattern having a line width of 30 μm was used. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds to develop, washed with water, and 220 in an oven. Post-baking was carried out at 20 ° C. for 20 minutes to prepare an evaluation substrate on which a line-and-space coloring pattern having a line width of 30 μm was formed.
When the film thickness of the formed colored pattern was measured, it was confirmed to be 1.4 μm.

<Evaluation of flatness>
The curable resin composition was applied to the evaluation substrate under the condition that the film thickness after post-baking was 1.5 μm using a spin coater. Then, it prebaked for 3 minutes at 100 degreeC in clean oven. After cooling, a coating film was formed by post-baking at 230 ° C. for 40 minutes.
Of the coating film on the evaluation substrate, the film thickness was measured at a portion where no colored pattern was formed under the coating film, and it was confirmed that the thickness was 1.5 μm.
The height difference of the undulation on the surface of the coating film formed on the colored pattern was measured. The results are shown in Table 3. If the height difference is 0.4 μm or less, the flatness of the coating film is good, and it can be said that it is particularly useful as a protective film for color filters.

[Table 3]

  From the results in Table 3, it was confirmed that the coating film formed from the curable resin composition of the present invention was excellent in heat resistance. Furthermore, it was confirmed that the coating film formed from the curable resin composition of the present invention was excellent in flatness.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition which can form the coating film which is excellent in various performances, such as transparency, heat resistance, and flatness.

Claims (5)

Derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, a monomer having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond a resin containing a structural unit, the resin is either of a resin [K1] and the resin [K2], and, seen containing a compound represented by the formula (1), a curable resin containing no polymerization initiator Composition.

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

[In Formula (a) and Formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
Resin [K1]: Copolymer of (a0) and (b0)
Resin [K2]: Copolymer of (a0), (b0) and (c0)
(A0) At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides
(B0) Monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond
(C0) A monomer different from (a0) and (b0) and copolymerizable therewith   The curable resin composition according to claim 1, wherein the content of the compound represented by the formula (1) is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the resin.   Furthermore, the curable resin composition of Claim 1 or 2 containing antioxidant. Coating film formed by the curable resin composition according to any one of claims 1 to 3.   A display device comprising the coating film according to claim 4.