JP5935276B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

In a liquid crystal display device or the like, a coating film such as a color filter protective film is used as a member. The color filter protective film is used for flattening surface irregularities caused by the underlying color filter or black matrix, or for protecting the color filter or the like from a chemical solution used to form these upper layer members. It is a coating film. In order to form the color filter protective film, a curable resin composition is used.
As such a curable resin composition, for example, a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and an aliphatic polycyclic epoxy compound, dipentaerythritol hexaacrylate and a solvent are mixed. A curable resin composition obtained in this manner is known (Patent Document 1).

JP 2009-149854 A

  When a coating film is formed on a color filter having a foreign matter of about several μm on the surface, a conical protrusion having a large skirt diameter may be formed around the foreign matter. If conical protrusions having a large diameter are formed on the coating film, the surface cannot be sufficiently flattened even if the protrusions are removed by polishing, which may cause display defects in the liquid crystal display device. When a conventionally proposed curable resin composition is used, when a coating film is formed on a color filter on which foreign matter of about several μm exists, the size of the diameter of the conical protrusion generated around the foreign matter is not necessarily limited. In some cases, it was not satisfactory.

The present invention provides the following [1] to [7].
[1] Curability including the following (A), (B) and (C), wherein the content of (B) is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A). Resin composition.
(A) including 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 compound selected from the group consisting of a silane compound having an amino group which may have a substituent and a silane compound having an imidazolyl group which may have a substituent (C )solvent

［式（Ｂ１）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を表し、該アルキル基に含まれる水素原子はアミノ基で置換されていてもよい。
Ｒ^６及びＲ^７は、互いに独立に、炭素数１〜４のアルキル基を表す。
Ｌ^１は、炭素数１〜６のアルカンジイル基を表す。
ｓは、２又は３を表す。複数のＲ^６は、互いに同一でも異なっていてもよい。］ [2] The curable resin composition according to [1], wherein the silane compound having an amino group which may have a substituent of (B) is a compound represented by the formula (B1).

[In Formula (B1), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and the hydrogen atom contained in the alkyl group is substituted with an amino group. May be.
R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
s represents 2 or 3. A plurality of R ⁶ may be the same as or different from each other. ]

[3] The curable resin composition according to [1], wherein the silane compound having an imidazolyl group which may have a substituent of (B) is a compound represented by the formula (B2).

[In Formula (B2), R ⁸ and R ⁹ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ² represents an alkanediyl group having 1 to 10 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group, and —CH ₂ — contained in the alkanediyl group is —O -Or -CO- may be substituted.
t represents 2 or 3. A plurality of R ¹⁰ may be the same or different from each other. ]

[4] The curable resin composition according to any one of [1] to [3], further including a polymerizable compound having an ethylenically unsaturated bond.
[5] The curable resin composition according to any one of [1] to [4], further including an epoxy resin (however, different from (A)).
[6] A coating film formed by applying the curable resin composition according to any one of [1] to [5] to a substrate and thermally curing the composition.
[7] A display device including the coating film according to [6].

  According to the curable resin composition of the present invention, even if a coating film is formed on a color filter having a foreign matter of about several μm on the surface, the diameter of the conical protrusion generated around the foreign matter is smaller. . Therefore, it is possible to reduce display defects of the liquid crystal display device by polishing the formed coating film and using it in the liquid crystal display device.

The curable resin composition of the present invention includes the following (A), (B) and (C), and the content of (B) is 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of (A). It is a curable resin composition having a mass part or less.
(A) including 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 compound selected from the group consisting of a silane compound having an amino group which may have a substituent and a silane compound having an imidazolyl group which may have a substituent (C ) Solvent In addition, 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 contains a resin (A). Resin (A) is a structural unit derived from 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 And a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).

As the resin (A) used in the curable resin composition of the present invention, for example,
Resin (A-1): a copolymer obtained by polymerizing (a) and (b), and resin (A-2): (a), (b), (a) and (b) Examples thereof include a copolymer obtained by polymerizing a copolymerizable monomer (c) (however, it does not have an oxiranyl group) (hereinafter sometimes referred to as “(c)”).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, 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 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.
Here, 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.

［式（ｂ−２）中、環Ｗ^０は脂環式炭化水素の環を表す。］
該脂環式炭化水素としては、シクロペンタン、シクロヘキサン及びシクロヘプタン等の単環の脂環式炭化水素；ノルボルナン、ジシクロペンタン及びトリシクロデカン等の橋かけ環の脂環式炭化水素が挙げられる。 Examples of (b) include a monomer (b-1) having a monocyclic oxirane ring and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b-1)”), and the following formula ( and a monomer (b-2) having a structure represented by b-2) and an ethylenically unsaturated bond (hereinafter may be referred to as “(b-2)”).

[In Formula (b-2), Ring W ⁰ represents an alicyclic hydrocarbon ring. ]
Examples of the alicyclic hydrocarbon include monocyclic alicyclic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; and bridged alicyclic hydrocarbons such as norbornane, dicyclopentane and tricyclodecane. .

  Specific examples of (b-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl 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 ( Glycidyloxymethi ) Styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4 Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

  Examples of (b-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclohexane). Mer 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), formula (II) ) And the like.

［式（Ｉ）及び式（ＩＩ）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、該アルキ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。
Ｘ^１及びＸ^２は、それぞれ独立に、単結合又は炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＮＲ^３−で置き換わっていてもよい。Ｒ^３は、水素原子又は炭素数１〜４のアルキル基を表す。］

[In Formula (I) and 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 or an alkanediyl group having 1 to 6 carbon atoms, and —CH ₂ — contained in the alkanediyl group is —O—, —S—, or —NR ^3. It may be replaced with-. R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

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.
Examples of the hydroxyalkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1 -Hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.
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, 1,4-butane-1,4-diyl group, pentane-1,5-diyl. Group, hexane-1,6-diyl group and the like.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. Among them, more preferably a single _{bond, *} - include CH ₂ CH 2 -O- group, more preferably a single _{bond, *} - include CH ₂ CH 2 -O- group.

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (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) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (I-1), formula (I-7), formula (I-9), and formula (I-15) can be mentioned.

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (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) The compound represented by either of these is mentioned.
More preferably, a compound represented by any one of formula (II-1), formula (II-7), formula (II-9), and formula (II-15) can be mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Moreover, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80 in the formula (I): formula (II). ~ 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 It is said to be nyl (meth) acrylate.
), Tricyclo [5.2.1.0 ^2,6 ] decan-3-en-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-4-ene-8- Yl (meth) acrylate (hereinafter referred to as dicyclopentenyl (meth) acrylate as a common name in the art), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate and the like ( (Meth) acrylic acid cyclic alkyl esters;
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;
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 [2.2 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, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, 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.
In addition to the above, (c) includes, for example, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond.

  Examples of the monomer having an oxetanyl group and an ethylenically unsaturated bond include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, and 3-ethyl-3-methacryloyloxy. Methyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl -3-acryloyloxyethyl oxetane and the like.

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

  Among these, as (c), cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, N-cyclohexylmaleimide and styrene are preferable.

In resin (A-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit constituting the resin (A-1).
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 resin (A-1) is in the above range, the storage stability of the curable resin composition and the chemical resistance, heat resistance, and mechanical strength of the resulting coating film are improved. Tend.
In the resin (A-1), (b) is preferably (b-2), and the ring W ⁰ in the formula (b-2) is a bridged alicyclic hydrocarbon ring ( b-2) is more preferable, and at least one selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is more preferable.

  Resin (A-1) 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 It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere while stirring. The method of heating and keeping warm is exemplified. 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. For example, as polymerization initiators, 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 (C) of the curable resin composition.

  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 (C) described later as the solvent in this polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In resin (A-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all structural units constituting the resin (A-2).
Structural unit derived from (a); 2-55 mol% (more preferably 5-45 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%)
When the ratio of the structural unit of the resin (A-2) is in the above range, the storage stability of the curable resin composition and the solvent resistance, heat resistance and surface hardness of the resulting coating film are improved. Tend.
In the resin (A-2), (b) is preferably (b-2), and the ring W ⁰ in the formula (b-2) is a bridged alicyclic hydrocarbon ring ( b-2) is more preferable, and at least one selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is more preferable.
Resin (A-2) can be manufactured by the same method as resin (A-1).

  Specific examples of the resin (A-1) include (meth) acrylic acid / copolymer of formula (I-1), (meth) acrylic acid / copolymer of formula (I-2), and (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), (meta ) Acrylic acid / copolymer of formula (I-9), (meth) acrylic acid / copolymer of formula (I-10), (meth) acrylic acid / copolymer of formula (I-11), ( (Meth) acrylic acid / copolymer of formula (I-12), (meth) acrylic acid / copolymer of formula (I-13), (meth) acrylic acid / copolymer of formula (I-14), (Meta) Copolymer of crylic acid / formula (I-15), copolymer of (meth) acrylic acid / formula (II-1), copolymer of (meth) acrylic acid / 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 / copolymer of formula (II-12), (meth) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / formula A copolymer of (II-14), a copolymer of (meth) acrylic acid / formula (II-15), a copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1), (Meth) acrylic acid / copolymer of formula (I-2) / formula (II-2), copolymer of (meth) acrylic acid / formula (I-3) / formula (II-3), (meta ) Acrylic acid / copolymer of formula (I-4) / formula (II-4), (meth) acrylic acid / copolymer of formula (I-5) / copolymer of formula (II-5), (meth) acrylic Acid / copolymer of formula (I-6) / formula (II-6), (meth) acrylic acid / copolymer of formula (I-7) / copolymer of formula (II-7), (meth) acrylic acid / Copolymer of formula (I-8) / formula (II-8), (meth) acrylic acid / copolymer of formula (I-9) / copolymer of formula (II-9), (meth) acrylic acid / formula ( I-10) / of formula (II-10) Copolymer, (meth) acrylic acid / copolymer of formula (I-11) / formula (II-11), (meth) acrylic acid / copolymer of formula (I-12) / formula (II-12) Coalesced, copolymer of (meth) acrylic acid / formula (I-13) / formula (II-13), copolymer of (meth) acrylic acid / formula (I-14) / formula (II-14), (Meth) acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth) acrylic acid / copolymer of formula (I-1) / formula (I-7), (meta ) Acrylic acid / copolymer of formula (I-1) / formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), Crotonic acid / copolymer of formula (I-3), crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5), crotonic acid / formula (I-6) ) Copolymer, Tonic acid / copolymer of formula (I-7), crotonic acid / copolymer of formula (I-8), crotonic acid / copolymer of formula (I-9), crotonic acid / formula (I-10) ), Crotonic acid / copolymer of formula (I-11), crotonic acid / copolymer of formula (I-12), crotonic acid / copolymer of formula (I-13), crotonic acid / Copolymer of formula (I-14), crotonic acid / copolymer of formula (I-15), crotonic acid / copolymer of formula (II-1), crotonic acid / copolymer of formula (II-2) Copolymer, crotonic acid / copolymer of formula (II-3), crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / formula (II-6) copolymer, crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9) Polymer, crotonic acid / copolymer of formula (II-10), crotonic acid / copolymer of formula (II-11), crotonic acid / copolymer of formula (II-12), crotonic acid / formula ( II-13), crotonic acid / copolymer of 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 / formula (I- 5), maleic acid / copolymer of formula (I-6), maleic acid / copolymer of formula (I-7), maleic acid / copolymer of formula (I-8), malein Acid / copolymer of formula (I-9), maleic acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), maleic acid / formula (I -12), maleic acid / copolymer of 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 / formula (II-4) ), Maleic acid / copolymer of formula (II-5), maleic acid / copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / Copolymer of formula (II-8), maleic acid / copolymer of formula (II-9), maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11) Copolymer, maleic acid / copolymer of formula (II-12), maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14) Polymer, 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 / formula (I-4) A copolymer of (meth) acrylic acid / maleic anhydride / copolymer of formula (I-5), a copolymer of (meth) acrylic acid / maleic anhydride / formula (I-6), (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-7), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-8), (meth) acrylic acid / maleic Acid anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-10) , (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic Acid / maleic anhydride / copolymer of formula (I-13), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-14), (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-15), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1), (meth) acrylic acid / maleic anhydride / formula (II-2) ), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-4), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-5), (meth) acrylic acid / ma Rain acid anhydride / copolymer of formula (II-6), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-7), (meth) acrylic acid / maleic anhydride / formula (II-8) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-9), (meth) acrylic acid / maleic anhydride / formula (II-10) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-11), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-12), ) Acrylic acid / maleic anhydride / copolymer of formula (II-13), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-14), (meth) acrylic acid / maleic acid And an anhydride / copolymer of formula (II-15).

  Specific examples of the resin (A-2) include a copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl ( Of (meth) acrylate, (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate Copolymer, 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.

  As the resin (A), a resin (A-) in which the total of the structural units derived from the resins (A-1) and (a) and the structural units derived from (b) is 90 mol% or more in all the structural units. 2) is preferable, and resin (A-1) is more preferable. These resins tend to be excellent in solvent resistance, heat resistance and surface hardness of the coating film.

  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. When the weight average molecular weight of the resin (A) is in the above range, the coating property 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 chemical resistance of the coating film tends to be excellent.

  The acid value of the resin (A) is from 30 mg-KOH / g to 180 mg-KOH / g, preferably from 40 mg-KOH / g to 150 mg-KOH / g, more preferably from 50 mg-KOH / g to 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 resin, and can be determined by titration using an aqueous potassium hydroxide solution.

The curable resin composition of the present invention may contain a resin (AX) different from the resin (A). As the resin (AX), for example,
Resin (A-3): a copolymer obtained by polymerizing (a) and (c),
Resin (A-4): a resin obtained by reacting (b) with a copolymer obtained by polymerizing (a) and (c),
Resin (A-5): Resins obtained by reacting (a) with a copolymer obtained by polymerizing (b) and (c).

In resin (A-3), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all structural units constituting the resin (A-3).
Structural unit derived from (a); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (c); 60 to 98 mol% (more preferably 65 to 95 mol%)
When the ratio of the structural unit of the resin (A-3) is in the above range, the storage stability of the curable resin composition and the solvent resistance of the coating film tend to be good.
Resin (A-3) can be manufactured by the same method as resin (A-1).

  Resin (A-4) and resin (A-5) can be manufactured through a two-step process, for example. In this case as well, the method described in the above-mentioned document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), JP-A-2001-2001 It can be produced with reference to the method described in JP 89533.

First, the resin (A-4) is obtained as a first step in the same manner as in the method for producing the resin (A-1) described above to obtain a copolymer of (a) and (c).
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder. Moreover, it is preferable to set it as the polystyrene conversion weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] similar to the said resin (A).
The ratio of the structural unit derived from (a) and the structural unit derived from (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%)
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%)

Next, as a second step, the carboxylic acid (a) and a part of the carboxylic anhydride derived from the obtained copolymer are reacted with the oxiranyl group (b) described above. Since the reactivity of the oxiranyl group is high and unreacted (b) hardly remains, (b-1) is preferable as (b) used in the production of the resin (A-4).
Specifically, following the above, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% (b) of a reaction catalyst of a carboxy group and an oxiranyl group with respect to the number of moles of (a) ( For example, tris (dimethylaminomethyl) phenol) is 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c), and a polymerization inhibitor (such as hydroquinone) is (a), 0.001-5 mass% is put in a flask with respect to the total amount of (b) and (c), and it is made to react at 60-130 degreeC for 1 to 10 hours, and resin (A-4) is obtained. it can. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the number of moles of (b) is preferably 10 to 75 mole%, more preferably 15 to 70 mole%, with respect to the number of moles of (a). By setting the number of moles of (b) within this range, the storage stability of the curable resin composition and the balance between the solvent resistance and heat resistance of the coating film tend to be improved.

Specific examples of the resin (A-4) include a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate, (meth) acrylic acid / benzyl ( Resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylate, resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic Resin obtained by reacting acid / styrene copolymer with glycidyl (meth) acrylate, resin obtained by reacting (meth) acrylic acid / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) Glycidyl (meth) acrylate was reacted with an acrylic acid / N-cyclohexylmaleimide copolymer. Fat, resin made by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meta ) Resin prepared by reacting acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene copolymer glycidyl (meth) acrylate , A resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / di Cyclopentanyl (meth) acrylate / N-cyclohexylmaleimi Copolymer glycidyl (meth) resins obtained by reacting an acrylate, glycidyl on copolymers of crotonic acid / dicyclopentanyl (meth) acrylate (meth) resins obtained by reacting acrylate;
Crotonic acid / benzyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / Styrene copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / Methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / N-cyclohexylmaleimide copolymer Resin in which glycidyl (meth) acrylate was reacted with the polymer, resin in which glycidyl (meth) acrylate was reacted with the copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, crotonic acid / di Cyclopentanyl (meth) acrylate / cycle A resin obtained by reacting a copolymer of hexyl (meth) acrylate with glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene with glycidyl (meth) acrylate, Crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide Resin obtained by reacting glycidyl (meth) acrylate with the coalescence;
Resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and resin obtained by reacting maleic acid / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate , A resin obtained by reacting maleic acid / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, a resin obtained by reacting maleic acid / styrene copolymer with glycidyl (meth) acrylate, maleic acid / maleic acid Resin prepared by reacting glycidyl (meth) acrylate with a copolymer of methyl, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / N-cyclohexylmaleimide, maleic acid / dicyclopentanyl (meth) Acrylate / benzyl (meth) acrylate copolymer Resin obtained by reacting ricidyl (meth) acrylate, resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, maleic acid / dicyclopenta Nyl (meth) acrylate / styrene copolymer reacted with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate copolymer reacted with glycidyl (meth) acrylate A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;
Resin obtained by reacting (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acrylate, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, Resin obtained by reacting a meth) acrylic acid / maleic anhydride / styrene copolymer with glycidyl (meth) acrylate, and a glycidyl (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate copolymer Resin reacted with (meth) acrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexylmale Resin prepared by reacting imide copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) ) Acrylate-reacted resin, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer, and glycidyl (meth) acrylate resin ( Resin made by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / maleic anhydride / dicyclopenta Nyl (meth) acrylate / methyl (meth) acrylate copolymer with glycidyl (meth) Resins obtained by reacting acrylate, (meth) resin obtained by reacting a copolymer glycidyl (meth) acrylate acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N- cyclohexyl maleimide;
Resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and (meth) acrylic acid / benzyl (meth) acrylate copolymer 3 , 4-Epoxycyclohexylmethyl methacrylate resin, (Meth) acrylic acid / cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate reaction resin, (Meth) acrylic acid / styrene A resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (4), a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / methyl (meth) acrylate, (Meth) acrylic acid / N-cyclohexyl male Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of imide, and 3,4-epoxy with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate A resin obtained by reacting cyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth ) A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / (meta ) 3, 4 in methyl acrylate copolymer A resin obtained by reacting epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;
Crotonic acid / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate; Crotonic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin in which methacrylate is reacted, Resin in which crotonic acid / cyclohexyl (meth) acrylate copolymer is reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / styrene copolymer in 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Crotonic acid / methyl crotonate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxycyclohexyl Methylme Resin in which acrylate was reacted, Crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate reacted in resin, crotonic acid / dicyclopentanyl A resin obtained by reacting a copolymer of (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene, 3,4 -Resin reacted with epoxycyclohexylmethyl methacrylate, Resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclo Pentanyl (Me ) Acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;
A resin obtained by reacting a maleic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and a maleic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on maleic acid / cyclohexyl (meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl on maleic acid / styrene copolymer Resin reacted with methacrylate, Resin reacted with 3,4-epoxycyclohexylmethyl methacrylate on copolymer of maleic acid / methyl maleate, 3,4-epoxycyclohexyl on copolymer of maleic acid / N-cyclohexylmaleimide Methylme Resin in which acrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, maleic acid / dicyclopentanyl Resin obtained by reacting (meth) acrylate / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; 3,4 for maleic acid / dicyclopentanyl (meth) acrylate / styrene copolymer -Resin obtained by reacting epoxycyclohexylmethyl methacrylate, resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate, maleic acid / dicyclohexane Pentanyl (Me ) Acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;
(Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / benzyl Resin obtained by reacting (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl Resin in which methyl methacrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / Copolymer of methyl (meth) acrylate with 3,4-epoxycyclohexene Resin reacted with silmethyl methacrylate, (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide copolymer, resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acid anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclo Resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of pentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate 3,4-epoxy on styrene / styrene copolymer 3,4-epoxycyclohexylmethyl methacrylate was added to a resin obtained by reacting cyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate. Examples include a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide. It is done.

Resin (A-5) obtains a copolymer of (b) and (c) as the first step in the same manner as in the method for producing resin (A-1) described above.
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder. Moreover, it is preferable to set it as the polystyrene conversion weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] similar to the said resin (A).
The ratio of the structural unit derived from (b) and the structural unit derived from (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, in the same manner as in the production method of the resin (A-4), the carboxylic acid or carboxylic acid that (a) has on the oxiranyl group derived from (b) in the copolymer of (b) and (c) It can be obtained by reacting an anhydride. A carboxylic acid anhydride may be further reacted with a hydroxy group generated by a reaction between an oxiranyl group and a carboxylic acid or carboxylic acid anhydride.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol% with respect to the number of moles of (b). Since the reactivity of the oxiranyl group is high and unreacted (b) hardly remains, (b-1) is preferred as (b) used in the production of the resin (A-5).

Specific examples of the resin (A-5) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, benzyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, resin in which (meth) acrylic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, styrene / glycidyl ( Resin obtained by reacting (meth) acrylic acid with a copolymer of (meth) acrylate, resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate, N-cyclohexyl A resin obtained by reacting (meth) acrylic acid with a maleimide / glycidyl (meth) acrylate copolymer Resin obtained by reacting clopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, and (meth) acrylic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate , (Dicyclopentanyl (meth) acrylate / Methyl (meth) acrylate / Glycidyl (meth) acrylate copolymer) Resin obtained by reacting (meth) acrylic acid, Dicyclopentanyl (meth) acrylate / N- Copolymerization of cyclohexylmaleimide / glycidyl (meth) acrylate Body (meth) resins obtained by reacting an acrylic acid;
Resin obtained by reacting crotonic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin obtained by reacting crotonic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting crotonic acid with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting styrene / glycidyl (meth) acrylate copolymer with crotonic acid, methyl crotonate / glycidyl Resin obtained by reacting crotonic acid with copolymer of (meth) acrylate, resin obtained by reacting crotonic acid with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin obtained by reacting crotonic acid with a copolymer of a rate, resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Resin obtained by reacting crotonic acid with a copolymer of nyl (meth) acrylate / styrene / glycidyl (meth) acrylate, croton into a copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate A resin obtained by reacting an acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;
Resin made by reacting maleic acid with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer, resin made by reacting maleic acid with benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin in which maleic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin in which maleic acid is reacted with a copolymer of styrene / glycidyl (meth) acrylate, methyl maleate / glycidyl Resin in which maleic acid is reacted with copolymer of (meth) acrylate, resin in which maleic acid is reacted with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / Glycidyl (Meth) Ac Resin in which maleic acid is reacted with a copolymer of a rate, resin in which maleic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer maleic resin, dicyclopentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate copolymer A resin obtained by reacting an acid, a resin obtained by reacting a dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with maleic acid;
Resin obtained by reacting dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin in which (meth) acrylic acid and maleic anhydride are reacted with, cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer in which (meth) acrylic acid and maleic anhydride are reacted, styrene Resin prepared by reacting (meth) acrylic acid and maleic anhydride with a copolymer of glycidyl / glycidyl (meth) acrylate, and (meth) acrylic acid and a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate Resin reacted with maleic anhydride, (N-cyclohexylmaleimide / glycidyl A resin obtained by reacting a (meth) acrylate copolymer with (meth) acrylic acid and maleic anhydride, a dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer ( Resin obtained by reacting meth) acrylic acid and maleic anhydride, (meth) acrylic acid and maleic anhydride into dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer , A resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, dicyclopentanyl (meth) Acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting polymer with (meth) acrylic acid and maleic anhydride, dimethypentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and maleic A resin reacted with an acid anhydride;
Resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin in which (meth) acrylic acid is reacted with the polymer, Resin in which (meth) acrylic acid is reacted with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, styrene / 3,4-epoxy A resin obtained by reacting (meth) acrylic acid with a copolymer of cyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, N-cyclohexylmaleimide / 3,4-epo A resin obtained by reacting a copolymer of cyclocyclohexylmethyl methacrylate with (meth) acrylic acid, a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (meta ) A resin obtained by reacting acrylic acid, a resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, Resin prepared by reacting a copolymer of pentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3 , 4-Epoxycyclohexylmethyl Resin of (meth) acrylic acid reacted with a copolymer of methacrylate, (meth) acrylic acid to a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Reacted resin;
A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, a copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate and croton Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, crotonic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer, croton Acid-reacted resin, Crotonic acid methyl / 3,4-epoxycyclohexylmethyl methacrylate copolymer, Crotonic acid-reacted resin, N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer A resin obtained by reacting crotonic acid, a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) A resin obtained by reacting crotonic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting crotonic acid with copolymer, resin obtained by reacting crotonic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle Resin obtained by reacting crotonic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;
Dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid reacted, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, maleic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer Resin in which acid is reacted, Resin in which maleic acid is reacted with copolymer of methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, Copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate A resin reacted with maleic acid, a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meta ) Resin prepared by reacting maleic acid with a copolymer of acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting maleic acid with copolymer, resin obtained by reacting maleic acid with copolymer of dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (Meta) acryle A resin obtained by reacting maleic acid with a copolymer of carbonate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate;
Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, benzyl (meth) acrylate / 3,4-epoxycyclohexyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of methyl methacrylate, (meth) acrylic acid and maleic acid with a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin in which anhydride is reacted, Resin in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of styrene / 3,4-epoxycyclohexylmethyl methacrylate, methyl (meth) acrylate / 3,4- Copolymerization of epoxycyclohexylmethyl methacrylate. A resin obtained by reacting (meth) acrylic acid and maleic anhydride, and a copolymer obtained by reacting a copolymer of N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride. , A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, dicyclopentanyl ( Resin of (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of tacrylate, copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid and maleic anhydride, and a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate to (meth) acrylic acid and Examples include resins reacted with maleic anhydride.

  The weight average molecular weight in terms of polystyrene of the resin (AX) is 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (AX) is in the above range, the coating property tends to be good.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (AX) 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 chemical resistance of the coating film tends to be excellent.

  The acid value of the resin (AX) is 30 to 180 mg-KOH / g, preferably 40 to 150 mg-KOH / g.

  When the resin (AX) is contained, the content thereof is 1% by mass or more and 60% by mass or less, preferably 1% by mass or more and 50% by mass with respect to the total amount of the resin (A) and the resin (AX). Hereinafter, it is more preferably 3% by mass or more and 40% by mass or less. When content of resin (AX) exists in the said range, there exists a tendency which is excellent in the adhesiveness of a coating film and a board | substrate, and the chemical resistance of a coating film.

  The total amount of the resin (A) and the resin (AX) is preferably 50 to 95% by mass, more preferably 55 to 90% by mass in the solid content of the curable resin composition of the present invention. When the total amount of the resin (A) and the resin (AX) is in the above range, the heat resistance of the coating film tends to be excellent. Here, solid content means the quantity remove | excluding the solvent (C) from curable resin composition.

  The curable resin composition of the present invention is at least one selected from the group consisting of a silane compound having an amino group which may have a substituent and a silane compound having an imidazolyl group which may have a substituent. (Hereinafter sometimes referred to as “silane compound (B)”). By including the silane compound (B) in the curable resin composition of the present invention, the diameter of the conical protrusion generated around the foreign matter is small even when a coating film is formed on the color filter where the foreign matter is present. .

  Examples of the amino group which may have a substituent include an amino group, an N-monosubstituted amino group, and an N, N′-disubstituted amino group. Examples of the substituent that the amino group may have include an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. And an acyl group having 2 to 12 carbon atoms.

Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, decyl group, dodecyl group, vinyl Group, allyl group, isopropenyl group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tricyclodecyl group, and a cyclohexenyl group.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, and a naphthyl group.
Examples of the acyl group having 2 to 12 carbon atoms include acetyl group, propionyl group, (meth) acryloyl group, hexylcarbonyl group and the like.

  The silane compound having an amino group which may have a substituent is preferably a compound represented by the formula (B1).

[In Formula (B1), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and the hydrogen atom contained in the alkyl group is substituted with an amino group. May be.
R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
s represents 2 or 3. A plurality of R ⁶ may be the same as or different from each other. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
Examples of the alkanediyl group having 1 to 6 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and butane-1,3. -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, etc. are mentioned.

As —NR ⁴ R ⁵ in formula (B1), an amino group and an alkyl group in which a hydrogen atom is substituted with an amino group (eg, a 3-aminopropyl group) are preferable. When the compound represented by the formula (B1) is a compound having —NH ₂ , it tends to be a conical protrusion having a smaller diameter when a coating film is formed on a color filter in which foreign matter is present.

R ⁶ and R ⁷ are preferably a methyl group and an ethyl group.
L ¹ is preferably an alkanediyl group having 3 to 6 carbon atoms, and more preferably a propanediyl group.
As s, 3 is preferable.

  Examples of the silane compound having an amino group which may have a substituent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyl. Methyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3- Examples include aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane. Of these, 3-aminopropyltrialkylsilanes such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane (the alkyl group preferably has 1 to 4 carbon atoms) are preferable.

  In the imidazolyl group which may have the above-mentioned substituent, examples of the substituent which the imidazolyl group may have include the same groups as the substituent which the amino group may have.

  The silane compound having an imidazolyl group which may have a substituent is preferably a compound represented by the formula (B2).

[In Formula (B2), R ⁸ and R ⁹ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ² represents an alkanediyl group having 1 to 10 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group, and —CH ₂ — contained in the alkanediyl group is —O -Or -CO- may be substituted.
t represents 2 or 3. A plurality of R ¹⁰ may be the same or different from each other. ]

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, decyl group, dodecyl group, vinyl Group, allyl group, isopropenyl group and the like.
Examples of the alkanediyl group having 1 to 10 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and butane-1,3. -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, 2-methylheptane-1,7-diyl group, octane-1,8-diyl Group, nonane-1,9-diyl group, decane-1,10-diyl group and the like.

  The silane compound having an imidazolyl group which may have a substituent is more preferably a compound represented by the formula (B2 ′).

[In Formula (B2 ′), R ¹² and R ¹³ each independently represent a hydrogen atom, a vinyl group, or an alkyl group having 1 to 20 carbon atoms.
R < ¹⁴ > represents a C1-C3 alkyl group mutually independently.
L ³ represents an alkanediyl group having 3 to 10 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group, and —CH ₂ — contained in the alkanediyl group is —O -Or -CO- may be substituted. ]

Examples of the alkyl group having 1 to 20 carbon atoms in R ¹² and R ¹³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, decyl, and dodecyl. Groups and the like.
R ¹² and R ¹³ are each independently preferably a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, More preferably, both are hydrogen atoms.
The alkyl group having 1 to 3 carbon atoms in R ^14, include those having 1 to 3 carbon atoms among the above. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
Examples of the alkanediyl group having 3 to 10 carbon atoms in L ³ include groups having 3 to 10 carbon atoms among those in L ² .

  The silane compound having an imidazolyl group which may have a substituent is more preferably a compound represented by the formula (B2 ″).

［式（Ｂ２’’）中、Ｒ^１５及びＲ^１６は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
Ｒ^１７は、互いに独立に、炭素数１〜３のアルキル基を表す。
Ｌ^４及びＬ^５は、互いに独立に、炭素数１〜７のアルカンジイル基を表す。ただし、Ｌ^４及びＬ^５を表すアルカンジイル基の合計炭素数は８以下である。］
Ｒ^１５及びＲ^１６は、水素原子が好ましい。
Ｒ^１７は、メチル基及びエチル基が好ましく、メチル基がより好ましい。
Ｌ^４及びＬ^５は、炭素数１〜５のアルカンジイル基が好ましく、炭素数２〜４のアルカンジイル基がより好ましい。

[In the formula (B2 ″), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R < ¹⁷ > represents a C1-C3 alkyl group mutually independently.
L ⁴ and L ⁵ each independently represent an alkanediyl group having 1 to 7 carbon atoms. However, the total carbon number of the alkanediyl group representing L ⁴ and L ⁵ is 8 or less. ]
R ¹⁵ and R ¹⁶ are preferably a hydrogen atom.
R ¹⁷ is preferably a methyl group or an ethyl group, and more preferably a methyl group.
L ⁴ and L ⁵ are preferably an alkanediyl group having 1 to 5 carbon atoms, and more preferably an alkanediyl group having 2 to 4 carbon atoms.

  Examples of the silane compound having an imidazolyl group which may have a substituent include IM-1000, IS-1000, YA-100, IC-100P, IA-100P (above, JX Nippon Mining & Metals Co., Ltd.) (Commercially available) can be used.

  Content of a silane compound (B) is 1-10 mass parts with respect to 100 mass parts of resin (A), Preferably it is 2-8 mass parts.

The curable resin composition of the present invention contains a solvent (C).
The solvent (C) is not particularly limited as long as it can dissolve each component contained in the curable resin composition of the present invention. 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, 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, ethylene glycol monomethyl ether acetate, ethylene glycol 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 solvents, organic solvents having a boiling point of 100 ° C. or more and 200 ° C. or less at 1 atm are preferable from the viewpoint of coating property and drying property. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3- A solvent containing at least one selected from the group consisting of ethyl ethoxypropionate, 3-methoxybutyl acetate and 3-methoxy-1-butanol is more preferable, and a solvent consisting of at least one selected from the above group is more preferable.

  The content of the solvent (C) in the curable resin composition of the present invention is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, based on the total amount of the curable resin composition of the present invention. -90 mass% is further more preferable. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 70% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass. When the content of the solvent (C) is in the above range, it is applied by a coating device such as a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), an inkjet, a roll coater, etc. Excellent applicability when applied.

  The curable resin composition of the present invention preferably contains an epoxy resin (D) (however, different from the resin (A)). The acid value of the epoxy resin (D) is preferably less than 30 mg-KOH / g. Here, the epoxy resin refers to a compound having two or more oxiranyl groups, or a mixture thereof, and is not limited to a polymer compound.

  Examples of the epoxy resin (D) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like.

  The content of the epoxy resin (D) is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the resin (A). Part or less is more preferable. When the content of the epoxy resin (D) is within the above range, the resulting coating film is excellent in flatness.

  The curable resin composition of the present invention preferably contains an antioxidant (E). Examples of the antioxidant (E) 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- tert-butyl-4-methylphenol, etc. Commercial products such as IRGANOX 3114 (manufactured by Ciba Japan Co., Ltd.) may be used, among which 1,3,5-tris (4-hydroxy-3,5-di -Tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, and by containing these antioxidants, the heat resistance of the resulting coating film is improved. There is a tendency to be good.

  The content of the antioxidant (E) is preferably 0.1% by mass or more and 5% by mass or less, and preferably 0.5% by mass or more and 3% by mass or less with respect to the total amount of the resin (A) and the resin (AX). Is more preferable. When the content of the antioxidant (E) is within the above range, heat resistance and pencil hardness are excellent. When the amount is less than 0.1% by mass, the heat resistance of the coating film tends to decrease, and when it exceeds 5% by mass, the pencil hardness of the coating film tends to decrease.

  The curable resin composition of the present invention preferably contains a polymerizable compound (F) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “polymerizable compound (F)”). The polymerizable compound having an ethylenically unsaturated bond is preferably a polymerizable compound 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”). The molecular weight of the polymerizable compound (F) is preferably 150 or more and 3000 or less, and more preferably 200 or more and 1500 or less. When 2 or more types of polymeric compounds (F) are included, it is preferable that the weight average molecular weight of the mixture is the said range.

  Examples of the compound having one ethylenically unsaturated bond include those mentioned in the above (a), (b) and (c), nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl. Examples thereof include carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.

  As compounds having two ethylenically unsaturated bonds, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Examples of compounds having 3 or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Hexa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone Modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol Tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, propylene oxide modified dipentaerythritol penta (meth) ) Acrylate, propylene oxide modified dipentaerythritol hexa (meth) acrylate, and the like.

  Among these, as the polymerizable compound (F), a compound having 3 or more ethylenically unsaturated bonds is preferable, and trimethylolpropane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable. When the polymerizable compound (F) is any of these compounds, the resulting coating film tends to be excellent in chemical resistance.

  When the polymerizable compound (F) is contained, the content is preferably 5 parts by mass or more and 90 parts by mass or less, and preferably 10 parts by mass or more with respect to 100 parts by mass of the total amount of the resin (A) and the resin (AX). 85 mass parts or less are more preferable, and 20 mass parts or more and 85 mass parts or less are still more preferable. When the content of the polymerizable compound (F) is in the above range, flatness and chemical resistance tend to be good.

  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, Toray 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.

  The content of the surfactant (G) is preferably 0.001% by mass to 0.2% by mass and more preferably 0.002% by mass to 0.1% by mass with respect to the curable resin composition. More preferred is 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in the above range, the flatness of the coating film can be improved.

  The curable resin composition of the present invention may contain an additive (H) such as a filler, other polymer compound, a thermal radical generator, an ultraviolet absorber, and a chain transfer agent, if necessary. .

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 dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

  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, preferably less than 1% by mass, more preferably less than 0.5% by mass.

  The curable resin composition of the present invention preferably has an average transmittance when filling a quartz cell having an optical path length of 1 cm and measuring the transmittance under a measurement wavelength of 400 to 700 nm using a spectrophotometer. Is 70% or more, 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, and 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 with respect to a coating film having a thickness of 2 μm after heat curing (for example, 150 to 240 ° C., 10 to 120 minutes). It is an average value when measured. Thereby, the coating film excellent in transparency in the visible light region can be provided.

The coating film 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, and plastic, and a color filter, various insulating films or conductive films, a drive circuit, and the like may be formed over the substrate.
The curable resin composition of the present invention can be applied onto a substrate by 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.
A coating film can be formed by post-baking the film from which volatile components have been removed at 150 to 240 ° C. for 10 to 120 minutes.
The film thickness of the coating film formed with the curable resin composition of this invention is not specifically limited, What is necessary is just to adjust suitably with the material to be used, a use, etc., for example, it is 0.1-10 micrometers.

  Thus, the obtained coating film is useful as an overcoat used for a liquid crystal display device or electronic paper, for example. Further, it can be used for a display device such as a touch panel. 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.

(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. for 4 hours using a dropping funnel.

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、固形分酸価は６０ｍｇ−ＫＯＨ／ｇであった。樹脂Ａａは、下記の構造単位を有する。

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 obtained resin Aa had a weight average molecular weight (Mw) of 8000, a molecular weight distribution (Mw / Mn) of 1.91, and a solid content acid value of 60 mg-KOH / g. Resin Aa 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 by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: mole of monomer (II-1)] A solution in which 240 parts of ratio = 50: 50} were dissolved in 140 parts of 3-methoxybutyl acetate 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 225 parts of 3-methoxybutyl acetate was placed in a flask over another 4 hours using another dropping funnel. 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 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 a solid content acid value of 113.9 mg-KOH / g. Resin Ab has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin Aa and resin Ab were measured under the following conditions using the GPC method.
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
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Example 1
The following components and solvent were mixed to obtain curable resin composition 1.
100 parts of resin Aa obtained in Synthesis Example 1 (in terms of solid content)
3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts bisphenol A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation)
10 parts 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (IRGANOX 3114 ; Manufactured by Ciba Japan Co., Ltd.) 1.0 part The solvent is a curable resin in which the mass ratio of propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and diethylene glycol ethyl methyl ether is 20:20:60. The composition 1 was mixed so that the solid content was 11%.

(Example 2)
A curable resin composition 2 was obtained in the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane was replaced with 3-aminopropyltriethoxysilane (KBE-903; manufactured by Shin-Etsu Chemical Co., Ltd.).

(Example 3)
A curable resin composition 3 was obtained in the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane was replaced with a compound represented by the following formula (IM-1000; manufactured by JX Nippon Mining & Metals). It was.

Example 4
The following components and solvent were mixed to obtain curable resin composition 4.
70 parts of resin Aa obtained in Synthesis Example 1 (in terms of solid content)
Dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku (
30 parts 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.)
5 parts bisphenol A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation)
10 parts 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (IRGANOX 3114 ; Manufactured by Ciba Japan Co., Ltd.) 1.0 part The solvent is a curable resin in which the mass ratio of propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and diethylene glycol ethyl methyl ether is 20:20:60. The composition 4 was mixed so that the solid content was 11%.

(Example 5)
A curable resin composition 5 was obtained in the same manner as in Example 4 except that the content of 3-aminopropyltrimethoxysilane was changed from 5 parts to 3 parts.

(Example 6)
A curable resin composition 6 was obtained in the same manner as in Example 4 except that the content of 3-aminopropyltrimethoxysila was changed from 5 parts to 10 parts.

(Comparative Example 1)
The following components and solvent were mixed to obtain a curable resin composition 7.
60 parts of resin Ab obtained in Synthesis Example 2 (in terms of solid content)
Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione (IRGANOX3114; manufactured by Ciba Japan Co., Ltd.) 0.8 part Solvent is propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy- The 1-butanol and 3-methoxybutyl acetate were mixed such that the mass ratio was 14: 20: 33: 33 and the solid content of the curable resin composition 7 was 11%.

<Viscosity measurement>
About the obtained curable resin composition, the viscosity was measured using the viscometer (model; TV-30; Toki Sangyo Co., Ltd. product), respectively. The results are shown in Table 1.

<Average transmittance 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.

<Average transmittance of coating film>
Using the obtained curable resin compositions 1 to 6, films were prepared under the following conditions so that the film thickness after curing was 3 μm, respectively.
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 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.
About the obtained film | membrane, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make). Higher transmittance means less absorption. The results are shown in Table 1.

<Measurement of conical protrusion on foreign object>
Acrylic beads having a diameter of 8 μm (trade name: Eposter YS77; manufactured by Nippon Shokubai Co., Ltd.) were dispersed in toluene to prepare a 0.01% dispersion. The dispersion was applied on a chromium thin film formed on a 15 cm square glass substrate with a spin coater to obtain a test substrate interspersed with acrylic beads.
The obtained curable resin composition was applied to the test substrate using a slit die coater (Takudai-100 manufactured by ITOCHU MACHINERY CO., LTD.) At a coating speed of 70 mm / sec. While adjusting the distance from the substrate and the like, the coating was applied so that the film thickness after curing was 1.5 μm. Then, it was dried with a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) until the degree of vacuum reached 0.5 torr. After prebaking on a hot plate at 90 ° C. for 2 minutes and further drying, post-baking was performed at 230 ° C. for 40 minutes to form a coating film.

  In the obtained coating film, conical protrusions were formed around acrylic beads scattered on the base test substrate. The protrusions were observed with a polarizing microscope (× 100 times), and the diameter of the outermost circumference of the Newton ring observed concentrically around the acrylic beads was measured. The diameter of the outermost periphery was taken as the diameter of the conical protrusion. The results are shown in Table 1.

  From the above results, it was confirmed that the curable resin composition of the present invention has a small diameter of the conical protrusion generated around the foreign matter even when a coating film is formed on the substrate on which the foreign matter is present.

  In the curable resin composition of the present invention, even when a coating film is formed on a color filter having a foreign matter of about several μm on the surface, the diameter of the conical protrusion generated around the foreign matter is small. Therefore, it is possible to reduce display defects of the liquid crystal display device by polishing the coating film formed from the curable resin composition of the present invention and using it in the liquid crystal display device.

Claims (7)

The curable resin composition containing the following (A), (B) and (C), wherein the content of (B) is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A). (However, it does not contain light-scattering substances.)
(A) including 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 compound selected from the group consisting of a silane compound having an amino group which may have a substituent and a silane compound having an imidazolyl group which may have a substituent (C )solvent The curable resin composition according to claim 1, wherein the silane compound having an amino group which may have a substituent of (B) is a compound represented by the formula (B1).

[In Formula (B1), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and the hydrogen atom contained in the alkyl group is substituted with an amino group. May be.
R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
s represents 2 or 3. A plurality of R ⁶ may be the same as or different from each other. ] The curable resin composition according to claim 1, wherein the silane compound having an imidazolyl group which may have a substituent of (B) is a compound represented by the formula (B2).

[In Formula (B2), R ⁸ and R ⁹ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 4 carbon atoms.
L ² represents an alkanediyl group having 1 to 10 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group, and —CH ₂ — contained in the alkanediyl group is —O -Or -CO- may be substituted.
t represents 2 or 3. A plurality of R ¹⁰ may be the same or different from each other. ]   Furthermore, the curable resin composition as described in any one of Claims 1-3 containing the polymeric compound which has an ethylenically unsaturated bond.   Furthermore, the curable resin composition as described in any one of Claims 1-4 containing an epoxy resin (however, different from (A)). Any one coating film formed from the curable resin composition according to claims 1-5.   A display device comprising the coating film according to claim 6.