JP2016166341A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of producing a cured film which can have good adhesion to a substrate.SOLUTION: The curable resin composition contains: a resin which contains a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer having a maleimide structure; and a compound having a group represented by formula (1) [where Rand Reach independently represent a 1-12C alkanediyl group, and * represents a bond].SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition.

In recent liquid crystal display devices, a curable resin composition is used to form a cured film such as a photo spacer or an overcoat. Such a curable resin composition includes, as a resin, only a copolymer of a compound having 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane structure and methacrylic acid. A thing is known (patent document 1).

JP 2010-202842 A

  In the curable resin composition described in Patent Document 1, when a coating film formed by applying the curable resin composition to a substrate is placed in a high-temperature and high-humidity environment, the adhesion between the coating film and the substrate is It was not always satisfactory.

The present invention includes the following inventions.
[1] A structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride,
A resin containing a structural unit derived from a monomer having a maleimide structure, and
Curable resin composition containing the compound which has group represented by Formula (1).

[In Formula (1), R ¹ and R ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. * Represents a bond. ]
[2] The curable resin composition according to [1], wherein the compound having a group represented by Formula (1) is an aromatic compound having a group represented by Formula (1).
[3] The curable resin composition according to [1] or [2], wherein the compound having a group represented by the formula (1) is a compound represented by the formula (2).

[In Formula (2), R ¹ and R ² represent the same meaning as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkylalkyl group having 3 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the cycloalkylalkyl group and the aralkyl group may be replaced by —O— or —S—. ]
[4] The curable resin composition according to [3], wherein R ³ has at least one epoxy group.
[5] The curable resin composition according to any one of [1] to [4], further comprising a compound having an epoxy group (however, different from a compound having a group represented by formula (1)). .
[6] A cured film comprising the curable resin composition according to any one of [1] to [5].
[7] A display device including the cured film according to [6].

  Even in a high-temperature and high-humidity environment, the cured film and the substrate made of the curable resin composition of the present invention can have good adhesion.

The curable resin composition of the present invention includes a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,
A resin containing a structural unit derived from a monomer having a maleimide structure (hereinafter sometimes referred to as resin (A)), and
A compound having a group represented by the formula (1) (hereinafter sometimes referred to as compound (1)) is included.

[In Formula (1), R ¹ and R ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. * Represents a bond. ]

The curable resin composition of the present invention further has a compound having an epoxy group (however, different from a compound having a group represented by the formula (1)) (hereinafter referred to as “epoxy group-containing compound (B)”). In some cases).
Furthermore, the curable resin composition of the present invention contains at least one selected from the group consisting of a polyvalent carboxylic acid (C), an antioxidant (D), a solvent (E) and a surfactant (G). Is more preferable.

<Compound (1)>
Compound (1) is a compound having a group represented by Formula (1).

[In Formula (1), R ¹ and R ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. * Represents a bond. ]

Examples of the alkanediyl group having 1 to 12 carbon atoms represented by R ¹ and R ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl and the like. Preferably it is a C1-C6 alkanediyl group.
Examples of the group represented by the formula (1) include a diglycidylamino group.

  The compound (1) is preferably an aromatic compound having a group represented by the formula (1) or an alicyclic compound having a group represented by the formula (1). Examples of the aromatic compound include compounds having a substituent represented by the formula (1) on benzene, biphenyl, naphthalene, anthracene, furan, thiophene, pyrrole, and the like. Examples of the alicyclic compound include compounds having a substituent represented by the formula (1) in cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Especially, it is a compound which has a substituent represented by Formula (1) in a C6-C12 aromatic compound, and it is more preferable that it is a compound represented by Formula (2).

[In Formula (2), R ¹ and R ² represent the same meaning as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkylalkyl group having 3 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the cycloalkylalkyl group and the aralkyl group may be replaced by —O— or —S—. However, —CH ₂ — contained in the oxacycloalkyl portion is not replaced. ]

The alkyl group having 1 to 12 carbon atoms represented by R ³ includes linear, branched and cyclic saturated hydrocarbon groups, and examples of the saturated hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the oxacycloalkylalkyl group having ³ to 18 carbon atoms represented by R ³ include an oxacyclopropylmethyl group, an oxacyclopropylethyl group, an oxacyclopropylpropyl group, an oxacyclopropylbutyl group, an oxacyclobutylmethyl group, An oxacyclobutylethyl group, an oxacyclopentylmethyl group, an oxacyclopentylethyl group, etc. are mentioned. Preferred is an oxacycloalkylalkyl group having 3 to 12 carbon atoms.
Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ³ include a benzyl group, a phenethyl group, and a phenylpropyl group. Preferably, it is an aralkyl group having 7 to 12 carbon atoms.
Examples of the substituent that the aralkyl group having 7 to 20 carbon atoms may have include one epoxy group, one glycidylamino group, one diglycidylamino group, one N-methylamino group, one N-ethylamino group, and the like. An amino group substituted with an alkyl group of ˜8; substituted with two alkyl groups of 1 to 8 carbon atoms such as N, N-dimethylamino group, N, N-diethylamino group, N, N-methylethylamino group, etc. Amino group; and the like.
—CH ₂ — contained in the oxacycloalkylalkyl group having ³ to 18 carbon atoms and the aralkyl group having 7 to 20 carbon atoms represented by R ³ may be replaced by —O— or —S—. -O- or -S- is also counted as carbon number.
R ³ may be any of the ortho, meta, and para positions with respect to the group represented by the formula (1), and is preferably the para position.

R ¹ and R ² preferably represent the same group.
R ³ preferably has at least one epoxy group,
It is more preferably an aralkyl group having 7 to 20 carbon atoms and an oxacycloalkylalkyl group having 3 to 18 carbon atoms having an epoxy group, a glycidylamino group or a diglycidylamino group.

  Examples of the compound (1) include a compound represented by the formula (1-1) to a compound represented by the formula (1-18). Preferably, the compound represented by Formula (1-1), the compound represented by Formula (1-2), the compound represented by Formula (1-5), and the compound represented by Formula (1-6) It is.

Two or more kinds of compounds (1) may be contained.
Content of compound (1) is 0.1-1000 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 0.1-100 mass parts, More preferably, it is 0.5- 10 parts by mass.
As compound (1), 1-1: N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline (EP-3950L: manufactured by ADEKA Corporation), EP-3950S (Made by ADEKA Co., Ltd.) etc. are marketed.

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

As (a), unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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, 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] bicyclounsaturated compounds containing a carboxy group such as 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] ;
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, (meth) acrylic acid and maleic anhydride are preferred, and (meth) acrylic acid is more preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

(B) refers to a polymerizable compound having a maleimide structure.
As monomers having a maleimide structure, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6- And monomers having a maleimide structure, such as maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide.
(B) is preferably N-phenylmaleimide, N-cyclohexylmaleimide, or N-benzylmaleimide.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl ( (Meth) acrylate, (Meth) acrylic acid esters such as adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclo unsaturated compounds;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoints of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from the respective monomers is relative to the total structural units constituting the resin [K1].
Structural unit derived from (a); 5 to 60 mol%
Structural unit derived from (b); 40-95 mol%
Is preferred,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural units constituting the resin [K1] is within the above range, the storage stability of the curable resin composition, the chemical resistance of the resulting cured film, the heat resistance, and the mechanical strength tend to be excellent. .

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

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

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

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2 to 40 mol%
Structural unit derived from (b); 2 to 80 mol%
Structural unit derived from (c); 10 to 96 mol%
It is preferable that
Structural unit derived from (a); 2 to 30 mol%
Structural unit derived from (b); 5-70 mol%
Structural unit derived from (c); 20-93 mol%
It is more preferable that
Moreover, the total amount with the structural unit derived from (c) is preferably 30 to 99 mol%, more preferably 50 to 99, based on the total number of moles of all structural units constituting the resin [K2]. Mol%.
When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable resin composition and the tendency of the cured film obtained to be excellent in adhesiveness, chemical resistance, heat resistance and mechanical strength tend to be obtained. is there.
Resin [K2] can be manufactured by the same method as resin [K1].

  Specific examples of the resin [K1] include a copolymer of (meth) acrylic acid / N-phenylmaleimide, a copolymer of (meth) acrylic acid / N-cyclohexylmaleimide, and (meth) acrylic acid / N-benzylmaleimide. A copolymer of (meth) acrylic acid / N-succinimidyl-3-maleimidobenzoate, a copolymer of (meth) acrylic acid / N-succinimidyl-4-maleimidobutyrate, (meth) acrylic acid / N-succinimidyl-6-maleimidocaproate copolymer, (meth) acrylic acid / N-succinimidyl-3-maleimide propionate copolymer, (meth) acrylic acid / N- (9-acridinyl) maleimide Copolymer, crotonic acid / N-phenylmaleimide copolymer, crotonic acid / N-cyclohexylmale Copolymer, crotonic acid / N-benzylmaleimide copolymer, crotonic acid / N-succinimidyl-3-maleimidobenzoate copolymer, crotonic acid / N-succinimidyl-4-maleimidobutyrate copolymer A copolymer of crotonic acid / N-succinimidyl-6-maleimidocaproate, a copolymer of crotonic acid / N-succinimidyl-3-maleimidopropionate, a copolymer of crotonic acid / N- (9-acridinyl) maleimide Polymer, maleic acid / N-phenylmaleimide copolymer, maleic acid / N-cyclohexylmaleimide copolymer, maleic acid / N-benzylmaleimide copolymer, maleic acid / N-succinimidyl-3-maleimidobenzoate Copolymer of maleic acid / N-succinimidyl-4-male Midobutyrate copolymer, maleic acid / N-succinimidyl-6-maleimidocaproate copolymer, maleic acid / N-succinimidyl-3-maleimidopropionate copolymer, maleic acid / N- (9- Acridinyl) maleimide copolymer, (meth) acrylic acid / maleic anhydride / N-phenylmaleimide copolymer, (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide copolymer, ) Acrylic acid / maleic anhydride / N-benzylmaleimide copolymer, (meth) acrylic acid / maleic anhydride / N-succinimidyl-3-maleimidobenzoate copolymer, (meth) acrylic acid / maleic acid Anhydride / N-succinimidyl-4-maleimidobutyrate copolymer, (meth) acrylic acid / Maleic anhydride / N-succinimidyl-6-maleimidocaproate copolymer, (meth) acrylic acid / maleic anhydride / N-succinimidyl-3-maleimidopropionate copolymer, (meth) acrylic And a copolymer of acid / maleic anhydride / N- (9-acridinyl) maleimide.

Specific examples of the resin [K2] include (meth) acrylic acid / N-phenylmaleimide / styrene copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / N-benzylmaleimide / styrene copolymer, crotonic acid / N-phenylmaleimide / styrene copolymer, crotonic acid / N-cyclohexylmaleimide / styrene copolymer, crotonic acid / N-benzylmaleimide / styrene copolymer Polymer, maleic acid / N-phenylmaleimide / styrene copolymer, maleic acid / N-cyclohexylmaleimide / styrene copolymer, maleic acid / N-benzylmaleimide / styrene copolymer, (meth) acrylic acid / Copolymer of maleic anhydride / N-phenylmaleimide / styrene, (meth) Acrylic acid / maleic anhydride / N- cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / maleic anhydride / N- benzyl maleimide / styrene copolymer,
(Meth) acrylic acid / N-phenylmaleimide / vinyltoluene copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / vinyltoluene copolymer, (meth) acrylic acid / N-benzylmaleimide / vinyltoluene Copolymer, crotonic acid / N-phenylmaleimide / vinyltoluene copolymer, crotonic acid / N-cyclohexylmaleimide / vinyltoluene copolymer, crotonic acid / N-benzylmaleimide / vinyltoluene copolymer, maleic Acid / N-phenylmaleimide / vinyltoluene copolymer, maleic acid / N-cyclohexylmaleimide / vinyltoluene copolymer, maleic acid / N-benzylmaleimide / vinyltoluene copolymer, (meth) acrylic acid / Maleic anhydride / N-phenylmaleimide / Vini Copolymer of toluene, copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide / vinyltoluene, copolymer of (meth) acrylic acid / maleic anhydride / N-benzylmaleimide / vinyltoluene Coalescence,
Copolymer of (meth) acrylic acid / N-phenylmaleimide / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / N-cyclohexylmaleimide / bicyclo [2.2.1] hept- 2-ene copolymer, (meth) acrylic acid / N-benzylmaleimide / bicyclo [2.2.1] hept-2-ene copolymer, crotonic acid / N-phenylmaleimide / bicyclo [2.2 .1] Copolymer of hept-2-ene, crotonic acid / N-cyclohexylmaleimide / bicyclo [2.2.1] copolymer of crotonic acid / N-benzylmaleimide / bicyclo [2 2.1] copolymer of hept-2-ene, maleic acid / N-phenylmaleimide / bicyclo [2.2.1] hept-2-ene copolymer, maleic acid / N-cyclohexyl Maleimide / bicyclo [2.2.1] hept-2-ene copolymer, maleic acid / N-benzylmaleimide / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic Copolymer of acid / maleic anhydride / N-phenylmaleimide / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide / bicyclo [2. 2.1] a copolymer of hept-2-ene, a copolymer of (meth) acrylic acid / maleic anhydride / N-benzylmaleimide / bicyclo [2.2.1] hept-2-ene,
(Meth) acrylic acid / N-phenylmaleimide / methyl (meth) acrylate copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / methyl (meth) acrylate copolymer, (meth) acrylic acid / N- Benzylmaleimide / methyl (meth) acrylate copolymer, crotonic acid / N-phenylmaleimide / methyl (meth) acrylate copolymer, crotonic acid / N-cyclohexylmaleimide / methyl (meth) acrylate copolymer, croton Acid / N-benzylmaleimide / methyl (meth) acrylate copolymer, maleic acid / N-phenylmaleimide / methyl (meth) acrylate copolymer, maleic acid / N-cyclohexylmaleimide / methyl (meth) acrylate copolymer Polymer, maleic acid / N-benzylmaleimi / Methyl (meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / N-phenylmaleimide / methyl (meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / N- Examples thereof include a copolymer of cyclohexylmaleimide / methyl (meth) acrylate and a copolymer of (meth) acrylic acid / maleic anhydride / N-benzylmaleimide / methyl (meth) acrylate.

The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 20,000. Particularly preferred is 5,000 to 10,000. When the weight average molecular weight of the resin (A) is in the above range, the applicability of the curable resin composition tends to be good.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the resulting cured film tends to be excellent in chemical resistance.

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

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

<Epoxy group-containing compound (B)>
The epoxy group-containing compound (B) is a compound different from the compound (1), and is preferably a resin containing an epoxy group.
The resin containing an epoxy group is not particularly limited except that it has a structure different from that of the resin (A), but at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin is preferable.

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

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

  The epoxy group-containing compound (B) is preferably an aromatic epoxy resin, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, and polyphenol type epoxy resin. More preferred is a glycidyl ether type epoxy resin, and more preferred is a bisphenol A type epoxy resin.

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

  When the epoxy group-containing compound (B) is an epoxy resin, the epoxy equivalent of the epoxy resin is preferably 100 to 500 g / eq, more preferably 150 to 400 g / eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. The epoxy equivalent can be measured by, for example, a method defined in JIS K7236.

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

The content of the epoxy resin is preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the total content of the resin (A) and the epoxy resin (B). When content of resin (A) exists in the said range, the cured film obtained tends to be excellent in adhesiveness with a board | substrate.
The total content of the resin (A) and the epoxy resin (B) is preferably 50 to 98% by mass, more preferably 55 to 85% by mass, based on the solid content of the curable resin composition of the present invention. It is. When the total content is in the above range, the resulting cured film tends to be excellent in chemical resistance.

<Polyvalent carboxylic acid (C)>
The curable resin composition of the present invention contains at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid (hereinafter sometimes referred to as “compound (C)”). Also good.
The polyvalent carboxylic acid (C) is at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid (C) is preferably 3000 or less, and more preferably 1000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecyl succinic anhydride, 2- (2 octa-3- Enyl) succinic anhydride, 2- (2,4,6-trimethylnon-3-enyl) succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. A chain polycarboxylic acid anhydride of
3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride , Norbornene dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2 2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, dicyclopentanetetracarboxylic acid diacid Alicyclic polycarboxylic acid anhydrides such as anhydrides;
Phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3'4,4'-diphenylsulfonetetra Carboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), glycerin tris (anhydro trimellitate), glycerin bis (anhydro trimellitate) monoacetate, 1,3,3a, 4,5,9b -Aromatic polycarboxylic acid anhydrides such as hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione;
ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by ADEKA Corporation), Rikacid-HH, same-TH, same-MH, same MH-700 (new Nippon Rika Co., Ltd.), Epikinia 126, same Commercial products such as YH-306 and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

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

  Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferred because of excellent heat resistance of the cured film, and transparency in the visible light region is particularly difficult to decrease. An acid anhydride is more preferable.

  The content of the polyvalent carboxylic acid (C) is preferably 0.1 to 100% by mass, more preferably 0.5 to 80% by mass, and still more preferably based on 100 parts by mass of the resin (A). Is 2 to 70% by mass. When the content of the polyvalent carboxylic acid (C) is within the above range, the cured film is excellent in heat resistance and adhesion.

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

Examples of phenolic antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methyl) Ruphenol), 2,2′-thiobis (6-tert-butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- (Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert- Butyl-4-methylphenol, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3 2] dioxaphosphepin and the like.
A commercial item may be used as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all are manufactured by BASF).

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

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

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

  Content of antioxidant (D) is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the resin (A). When the content of the antioxidant (D) is within the above range, the resulting cured film tends to be excellent in heat resistance and pencil hardness.

  The curable resin composition of the present invention further has a 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) acrylic compound (F)”). May be included.

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

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

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

  The content of the (meth) acrylic compound (F) is preferably 20 to 100 parts by mass, more preferably 25 to 70 parts by mass with respect to 100 parts by mass of the resin (A). If the content of the (meth) acrylic compound (F) is in the above range, the resulting cured film tends to have good chemical resistance and mechanical strength.

<Solvent (E)>
Solvent (E) is 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—), ether ester Solvent (solvent containing —COO— and —O— in the molecule), ketone solvent (solvent containing —CO— in the molecule and not containing —COO—), alcohol solvent, aromatic hydrocarbon solvent, amide solvent And dimethyl sulfoxide.

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

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

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

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

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

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

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

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

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

<Surfactant (G)>
Examples of the surfactant (G) include silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, and the like.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

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

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

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

<Other ingredients>
The curable resin composition of the present invention may contain additives such as a filler, a thermal radical generator, an ultraviolet absorber, a chain transfer agent, and an adhesion promoter as necessary.

  Examples of the filler include glass, silica, and alumina.

Specific examples of the thermal radical generator include 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.
As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyl Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl)- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc. Is mentioned.

  The curable resin composition of the present invention contains substantially no photopolymerization initiator. That is, in the curable resin composition of the present invention, the content of the photopolymerization initiator relative to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass, more preferably less than 0.1% by mass. It is. Examples of the photopolymerization initiator include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds.

  Moreover, the curable resin composition of this invention does not contain colorants, such as a pigment and dye, substantially. That is, in the curable resin composition of the present invention, the content of the colorant with respect to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

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

  In the cured film comprising the curable resin composition of the present invention, the average transmittance of the cured film is preferably 80% or more, and more preferably 90% or more. This average transmittance is measured under the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer with respect to a cured film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured below. Thereby, the cured film excellent in transparency in the visible light region can be provided.

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

<The manufacturing method of the cured film of this invention>
The cured film which consists of a curable resin composition of this invention is obtained by apply | coating the curable resin composition of this invention on a board | substrate, and making it harden | cure with a heat | fever.
Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed over the substrate.
Coating on the substrate is preferably performed using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.

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

  The cured film thus obtained is useful as a protective film or overcoat for color filters and touch panels used in liquid crystal display devices, organic EL display devices and electronic paper.

  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>
The inside of the flask equipped with a reflux condenser, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, and 230 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Next, a mixed solution of 40 parts of acrylic acid, 360 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8 and 9-yl acrylate, and 85 parts of propylene glycol monomethyl ether acetate was added. It was dripped over 5 hours.
On the other hand, a mixed solution prepared by dissolving 55 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 230 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was held at the same temperature for 4 hours, and then cooled to room temperature. A copolymer (resin having a B-type viscosity (23 ° C.) of 465 mPas, a solid content of 43.5% by mass, and a solution acid value of 23 mg-KOH / g Aa) was obtained. The produced resin Aa had a weight average molecular weight (Mw) of 7,200 and a dispersity of 1.9.

<Synthesis Example 2>
The inside of the flask equipped with a reflux condenser, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, 207 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 63 parts of methacrylic acid, 209 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8 and 9-yl acrylate, 78 parts of phenylmaleimide, 140 of propylene glycol monomethyl ether acetate Part of the mixed solution was added dropwise over 5 hours.
Meanwhile, a mixed solution prepared by dissolving 51 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 252 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was held at the same temperature for 3 hours, and then cooled to room temperature. A copolymer (resin having a B-type viscosity (23 ° C.) of 1820 mPas, a solid content of 39.5% by mass, and a solution acid value of 34 mg-KOH / g Ac) was obtained. The produced resin Ac had a weight average molecular weight (Mw) of 9400 and a dispersity of 2.2.

<Synthesis Example 3>
The inside of the flask equipped with a reflux condenser, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere, and 23 parts of ethyl lactate and 210 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. Next, a mixed solution of 28 parts of acrylic acid, 182 parts of cyclohexylmaleimide, and 476 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours.
Meanwhile, a mixed solution prepared by dissolving 3 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours.
After completion of dropping, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature, and a copolymer (resin having a B-type viscosity (23 ° C.) of 19 mPas, a solid content of 21.9% by mass, and a solution acid value of 21 mg-KOH / g Ad) was obtained. The produced resin Ad had a weight average molecular weight (Mw) of 10900 and a dispersity of 2.4.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as the dispersity.

Examples 1 to 8 and Comparative Examples 1 and 2
<Preparation of curable resin composition>
As shown in Table 1, each component was mixed at the stated ratio to obtain a curable resin composition.

In Table 1, the resin content represents a mass part in terms of solid content.
Resin (Aa): Resin obtained in Synthesis Example 1 Resin (Ac): Resin obtained in Synthesis Example 3 Resin (Ad): Resin obtained in Synthesis Example 4 Epoxy group-containing compound (B): Bisphenol A type Epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Corporation)
Compound (1): 1-1: N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline (EP-3950S: manufactured by ADEKA Corporation)
Compound (1): 1-2: 4,4′-methylenebis [N, N-bis (oxiranylmethyl) aniline] (manufactured by SYNASIA)
Compound (X): Monoallyl diglycidyl isocyanuric acid (MA-DGIC: manufactured by Shikoku Chemicals Co., Ltd.)
Polyvalent carboxylic acid (C): 1,2,3,6-tetrahydrophthalic anhydride (Licacid TH; manufactured by Shin Nippon Rika Co., Ltd.)
Antioxidant (F); 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trione (IRGANOX (registered trademark) 3114; manufactured by BASF)
Surfactant (H); Megafac (registered trademark) F554 (manufactured by DIC Corporation)
Solvent (E): Ea: Propylene glycol monomethyl ether acetate Solvent (E): Eb: Ethyl lactate In the solvent (E), the solid content of the curable resin composition becomes “solid content (%)” in Table 1. Mixed.

<Production of cured film>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and isopropanol and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after post-baking was 1.5 μm, and then pre-baked at 100 ° C. for 3 minutes in a clean oven. Thereafter, post-baking was performed at 230 ° C. for 40 minutes to obtain a cured film.

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

<Adhesion>
The cured film obtained above was subjected to a pressure cooker test (temperature 120 ° C., humidity 100%, pressure 2 atm; saturated pressure cooker PC-305S; manufactured by Hirayama Seisakusho Co., Ltd.) for 2 hours, and then JIS K-5400. -1990. 8.5.3 Adhesiveness Adhesiveness of the cured film to the glass substrate was evaluated by a cross-cut tape method. Table 100 shows the number of grids in which 95% or more of the cured film clearly remains on the substrate among 100 grids as adhesion (pieces).

  The cured film comprising the curable resin composition of the present invention exhibits good adhesion to the substrate even in a high-temperature and high-humidity environment, so it can be used as a cured film for photo spacers and overcoats in liquid crystal display devices. can do.

Claims (7)

A structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride;
A resin containing a structural unit derived from a monomer having a maleimide structure, and
Curable resin composition containing the compound which has group represented by Formula (1).

[In Formula (1), R ¹ and R ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. ]   The curable resin composition according to claim 1, wherein the compound having a group represented by the formula (1) is an aromatic compound having a group represented by the formula (1). The curable resin composition according to claim 1 or 2, wherein the compound having a group represented by formula (1) is a compound represented by formula (2).

[In Formula (2), R ¹ and R ² represent the same meaning as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkylalkyl group having 3 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the cycloalkylalkyl group and the aralkyl group may be replaced by —O— or —S—. ] The curable resin composition according to claim 3, wherein R ³ is a group having at least one epoxy group.   Furthermore, the curable resin composition in any one of Claims 1-4 containing the compound (However, it differs from the compound which has group represented by Formula (1)) which has an epoxy group.   A cured film comprising the curable resin composition according to claim 1.   A display device comprising the cured film according to claim 6.