JP6819051B2 - Curable resin composition - Google Patents

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 a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane structure and methacrylic acid. A thing is known (Patent Document 1).

JP-A-2010-20842

In the curable resin composition described in Patent Document 1, when the 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 high. , Was not always fully satisfactory.

The present invention includes the following inventions.
[1] Structural units derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and
A resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond, and
A curable resin composition containing a compound having a group represented by the formula (1).

[In the 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 the formula (1) is an aromatic compound having a group represented by the 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 the formula (2), R ¹ and R ² have the same meanings as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkyl alkyl group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and the oxa. The -CH _2- contained in the cycloalkylalkyl group and the aralkyl group may be replaced with -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 the compound having a group represented by the formula (1)). ..
[6] Structural units derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
A resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond
The curable resin composition according to any one of [1] to [5], which is a resin containing a structural unit derived from a monomer having a maleimide structure.
[7] A cured film made of the curable resin composition according to any one of [1] to [6].
[8] A display device including the cured film according to [7].

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

The curable resin composition of the present invention is
Structural units derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
A resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond (hereinafter, may be referred to as resin (A)), and
A compound having a group represented by the formula (1) (hereinafter, may be referred to as compound (1)) is included.

[In the 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 is further referred to as a compound having an epoxy group (however, it is different from a compound having a group represented by the formula (1)) (hereinafter, referred to as "epoxy group-containing compound (B)". In some cases), it is preferable to include.
Further, 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)>
The compound (1) is a compound having a group represented by the formula (1).

[In the 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 can be mentioned. It is preferably an alkanediyl group having 1 to 6 carbon atoms.
Examples of the group represented by the formula (1) include a diglycidylamino group and the like.

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) in 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, cyclooctane and the like. Among them, preferably, an aromatic compound having 6 to 12 carbon atoms includes a compound having a substituent represented by the formula (1), and more preferably a compound represented by the formula (2).
The compound (1) is more preferably a compound represented by the formula (2).

[In the formula (2), R ¹ and R ² have the same meanings as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkyl alkyl group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and the oxa. The -CH _2- contained in the cycloalkylalkyl group and the aralkyl group may be replaced with -O- or -S-. However, -CH _2- contained in the oxacycloalkyl moiety does not replace. ]

The alkyl group having 1 to 12 carbon atoms represented by R ³ contains a linear, branched and cyclic saturated hydrocarbon group, and the saturated hydrocarbon group includes a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples thereof include a group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.
Examples of the oxacycloalkylalkyl group having ³ to 18 carbon atoms represented by R3 include an oxacyclopropylmethyl group, an oxacyclopropylethyl group, an oxacyclopropylpropyl group, an oxacyclopropylbutyl group, and an oxacyclobutylmethyl group. Examples thereof include an oxacyclobutylethyl group, an oxacyclopentylmethyl group and an oxacyclopentylethyl group. It is preferably 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, a phenylpropyl group and the like. It is preferably an aralkyl group having 7 to 12 carbon atoms.
As the substituent which the aralkyl group having 7 to 20 carbon atoms may have, one carbon number 1 such as an epoxy group; a glycidylamino group; a diglycidylamino group; an N-methylamino group and an N-ethylamino group Amino group substituted with an alkyl group of ~ 8; substituted with two alkyl groups having 1 to 8 carbon atoms such as N, N-dimethylamino group, N, N-diethylamino group, N, N-methylethylamino group. Amino group; etc.
-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 R3 may be replaced by -O- or -S-, and is replaced. Also, -O- or -S- is counted as the number of carbon atoms.
R ³ may be in the ortho position, the meta position, or the para position with respect to the group represented by the formula (1), and is preferably in the para position.

R ¹ and R ² preferably represent the same group.
R ³ preferably has at least one epoxy group, and is 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. Is more preferable.

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 the formula (1-1), the compound represented by the formula (1-2), the compound represented by the formula (1-5) and the compound represented by the formula (1-6) are preferable. Is.

The compound (1) may contain two or more kinds.
The content of the compound (1) is usually 0.1 to 1000 parts by mass, preferably 0.1 to 100 parts by mass, and more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the resin (A). It is 80 parts by mass, more preferably 2 to 70 parts.
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 Corporation) and the like are commercially available.

<Resin (A)>
The resin (A) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, may be referred to as “(a)”).
It is a resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”).
The resin (A) further has a structural unit derived from a monomer (hereinafter sometimes referred to as “(c)”) which is different from (a) and (b) and can be copolymerized with them. You may.
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-, 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-cyclohexendicarboxylic 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 A bicyclounsaturated compound containing a carboxy group such as [2.2.1] hept-2-ene and 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 divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. ;
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, maleic anhydride and the like are preferable, and (meth) acrylic acid is more preferable, from the viewpoint of copolymerizability and solubility in an alkaline aqueous solution.
In addition, in this specification, "(meth) acryloyl" represents at least one kind 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 cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
Examples of the cyclic ether structure having 2 to 4 carbon atoms include at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring.
In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.

As (b), a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b1)”),
Monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"),
Examples thereof include a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b3)”).

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

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene , 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

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

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

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
^Examples of R ^b1 and R ^b2 include 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.

The alkanediyl group having 1 to 6 carbon atoms in R ^b3 includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentan-. Examples thereof include a 1,5-diyl group and a hexane-1,6-diyl group, preferably a methylene group and an ethylene group.
^Examples of X ^b1 and X ^b2 preferably include a single bond, a methylene group, an ethylene group, * -CH _2- O- and * -CH ₂ CH _2- O-, and more preferably a single bond and * -CH _2. CH _2- O-can be mentioned (* represents a bond with O).

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

Examples of the compound represented by the formula (II) include a compound represented by the formula (II-1) to a compound represented by the formula (II-15). Among them, the compound represented by the formula (II-1), the compound represented by the formula (II-3), the compound represented by the formula (II-5), and the compound represented by the formula (II-7). A compound represented by any of a compound represented by the formula (II-9) and a compound represented by the formula (II-11) to a compound represented by the formula (II-15) is preferable.
Any of a compound represented by the formula (II-1), a compound represented by the formula (II-7), a compound represented by the formula (II-9), and a compound represented by the formula (II-15). The compound represented by is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or mixed in an arbitrary ratio. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is based on a molar basis, preferably 5:95 to 95: 5, and more preferably 10:90 to. It is 90:10, more preferably 20:80 to 80:20.

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

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

As (b), (b1) is preferable in that the reliability of the obtained curable resin composition such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the curable resin composition has excellent storage stability.

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 ] Decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl ( (Meta) acrylates such as adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and 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, and diethyl itaconic acid;
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 (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Maleimide propionate and N- (9-acridinyl) Maleimide and other monomers having a maleimide structure;
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 and 2,3-dimethyl-1,3-butadiene and the like can be mentioned.
Of these, monomers having a styrene, vinyltoluene and maleimide structures are preferable from the viewpoint of copolymerization reactivity and heat resistance, and styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and Bicyclo [2.2.1] hept-2-ene is more preferred.

In the resin [K1], the ratio of the structural units derived from each monomer is based on the total structural units constituting the resin [K1].
Structural unit derived from (a); 5-60 mol%
Structural unit derived from (b); 40-95 mol%
Is preferable
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 curable resin composition tends to be excellent in storage stability, chemical resistance of the obtained cured film, heat resistance and mechanical strength. ..

Resin [K1] can be used, for example, in the method described in the document "Design of Experiments for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be manufactured with reference to the cited references described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) The solvent may be any solvent that dissolves each monomer, and examples of the solvent for the curable resin composition include the solvent (E) described later.

As the obtained resin, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a resin taken out as a solid (powder) by a method such as reprecipitation may be used. You may use it. In particular, by using the solvent (E) described later as the solvent in this polymerization, the solution after the reaction can be used as it is in 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 is determined in the total structural units constituting the resin [K2].
Structural unit derived from (a); 2-40 mol%
Structural unit derived from (b); 2-80 mol%
Structural unit derived from (c); 10-96 mol%
Is preferable,
Structural unit derived from (a); 2-30 mol%
Structural unit derived from (b); 5-50 mol%
Structural unit derived from (c); 20-93 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the curable resin composition tends to be excellent in storage stability, adhesiveness of the obtained cured coating film, chemical resistance, heat resistance and mechanical strength. There is.
The resin [K2] can be produced by the same method as the resin [K1].

As a specific example of the resin [K1], a compound represented by (meth) acrylic acid / formula (I-1) (hereinafter, may be abbreviated as “formula (I-1)”. Formula (I-2). The same applies to the above, etc.), (meth) acrylic acid / copolymer of formula (I-2), (meth) acrylic acid / copolymer of formula (I-3), (meth). ) Acrylic acid / copolymer of formula (I-4), (meth) acrylic acid / copolymer of formula (I-5), (meth) acrylic acid / copolymer of formula (I-6), ( Meta) Acrylic Acid / Copolymer of Formula (I-7), (Meta) Acrylic Acid / Copolymer of Formula (I-8), (Meta) Acrylic Acid / Copolymer of Formula (I-9), (Meta) Acrylic Acid / Copolymer of Formula (I-10), (Meta) Acrylic Acid / Copolymer of Formula (I-11), (Meta) Acrylic Acid / Copolymer of Formula (I-12) , (Meta) acrylic acid / copolymer of formula (I-13), (meth) acrylic acid / copolymer of formula (I-14), (meth) acrylic acid / copolymer of formula (I-15) Combined, (meth) acrylic acid / copolymer of formula (II-1), (meth) acrylic acid / copolymer of formula (II-2), (meth) acrylic acid / copolymer of formula (II-3) Polymer, (meth) acrylic acid / copolymer of formula (II-4), (meth) acrylic acid / copolymer of formula (II-5), (meth) acrylic acid / formula (II-6) Copolymer, (meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / copolymer of formula (II-8), (meth) acrylic acid / formula (II-9) Copolymer, (meth) acrylic acid / copolymer of formula (II-10), (meth) acrylic acid / copolymer of formula (II-11), (meth) acrylic acid / formula (II-12) ), (Meta) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / copolymer of formula (II-14), (meth) acrylic acid / formula (II-) 15) Copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) copolymer, (meth) acrylic acid / formula (I-2) / formula (II-2) Copolymer, (meth) acrylic acid / formula (I-3) / formula (II-3) copolymer, (meth) acrylic acid / formula (I-4) / formula (II-4) Polymer, (meth) acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth) acrylic acid / copolymer of formula (I-6) / formula (II-6) , (Meta) acrylic acid / copolymer of formula (I-7) / formula (II-7), (meth) acrylic acid / copolymer of formula (I-8) / formula (II-8), ( Meta) Acrylic acid / formula (I-9) / copolymer of formula (II-9), (meth) crotonic acid / copolymer of formula (I-10) / formula (II-10), (meth) crotonic acid / formula (I) -11) / Crotonic acid of formula (II-11), (meth) crotonic acid / copolymer of formula (I-12) / formula (II-12), (meth) crotonic acid / formula (I-13) ) / Copolymer of formula (II-13), (meth) crotonic acid / copolymer of formula (I-14) / formula (II-14), (meth) crotonic acid / formula (I-15) / Copolymer of formula (II-15), (meth) crotonic acid / copolymer of formula (I-1) / formula (I-7), (meth) crotonic acid / formula (I-1) / formula ( II-7) copolymer, crotonic acid / formula (I-1) copolymer, crotonic acid / formula (I-2) copolymer, crotonic acid / formula (I-3) copolymer , Crotonic acid / formula (I-4) copolymer, crotonic acid / formula (I-5) copolymer, crotonic acid / formula (I-6) copolymer, crotonic acid / formula (I-) 7) Crotonic acid / Crotonic acid / Formula (I-8) copolymer, Crotonic acid / Formula (I-9) copolymer, Crotonic acid / Formula (I-10) copolymer, Crotonic acid Acid / formula (I-11) copolymer, crotonic acid / formula (I-12) copolymer, crotonic acid / formula (I-13) copolymer, crotonic acid / formula (I-14) Crotonic acid / Crotonic acid / formula (I-15) copolymer, crotonic acid / formula (II-1) copolymer, crotonic acid / 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), corotonic acid / copolymer of formula (II-6) Polymer, crotonic acid / formula (II-7) copolymer, crotonic acid / formula (II-8) copolymer, crotonic acid / formula (II-9) copolymer, crotonic acid / formula (II-9) II-10) copolymer, crotonic acid / formula (II-11) copolymer, crotonic acid / formula (II-12) copolymer, crotonic acid / formula (II-13) copolymer , Crotonic acid / formula (II-14) copolymer, crotonic acid / formula (II-15) copolymer, crotonic acid / formula (I-1) copolymer, maleic acid / formula (I-) 2) Crotonic acid, maleic acid / formula (I-3) copolymer, maleic acid / formula (I-4) copolymer, maleic acid / formula (I-5) copolymer, malein Acid / formula (I-6) copolymer, maleic acid / formula (I-7) copolymer, maleic acid / formula (I-8) copolymer, maleic acid / formula (I-9) Copolymer, Ma Laic acid / formula (I-10) copolymer, maleic acid / formula (I-11) copolymer, maleic acid / formula (I-12) copolymer, maleic acid / formula (I-13) ), Maleic acid / formula (I-14) copolymer, maleic acid / formula (I-15) copolymer, maleic acid / formula (II-1) copolymer, maleic acid / Copolymer of formula (II-2), maleic acid / copolymer of formula (II-3), maleic acid / copolymer of formula (II-4), maleic acid / copolymer of formula (II-5) Copolymer, maleic acid / copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / copolymer of formula (II-8), maleic acid / formula (II-9) copolymer, maleic acid / formula (II-10) copolymer, maleic acid / formula (II-11) copolymer, maleic acid / formula (II-12) copolymer Combined, maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / copolymer of formula (II-15), (meth) acrylic acid / Maleic acid anhydride / copolymer of formula (I-1), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-2), (meth) acrylic acid / maleic acid anhydride / formula The copolymer of (I-3), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic acid anhydride / formula (I-5) Copolymer, (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-6), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-7), (meth) ) Acrylic acid / maleic acid anhydride / copolymer of formula (I-8), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic acid Anhydrous / copolymer of formula (I-10), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-11), (meth) acrylic acid / maleic acid anhydride / formula (I) -12) copolymer, (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-13), (meth) acrylic acid / maleic acid anhydride / common weight of formula (I-14) Combined, (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-15), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-1), (meth) acrylic Acid / maleic acid anhydride / copolymer of formula (II-2), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-3), (meth) acrylic acid / maleic acid anhydride / Co-weight of equation (II-4) Combined, (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-5), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-6), (meth) acrylic Acid / maleic acid anhydride / copolymer of formula (II-7), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-8), (meth) acrylic acid / maleic acid anhydride / Copolymer of formula (II-9), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-10), (meth) acrylic acid / maleic acid anhydride / formula (II-11) ), (Meta) acrylic acid / maleic acid anhydride / copolymer of formula (II-12), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-13), Examples thereof include (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-14), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-15), and the like.

Specific examples of the resin [K2] include (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-2) / methyl (meth). Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate, common weight of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate Combined, (meth) acrylic acid / formula (I-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate copolymer, (meth) ) Acrylic acid / formula (I-7) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / A copolymer of formula (I-9) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-). 11) / Methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-12) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-13) / methyl (Meta) acrylate copolymer, (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate , (Meta) acrylic acid / formula (II-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate copolymer , (Meta) acrylic acid / formula (II-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate copolymer, (meth) Acrylic acid / formula (II-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-9) ) / Methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-11) / methyl ( Copolymer of meta) acrylate, (meth) acrylic acid / formula (II-12) / methyl (meth) acryle Co-polymer of (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate, co-polymer of (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate Copolymer of polymer, (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate common weight Combined, (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclo Copolymer of pentanyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (I-1) / dicyclopentanyl (meth) ) Acrylic acid copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate copolymer, (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) / Copolymer of dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / copolymer of dicyclopentanyl (meth) acrylate, (meth) Acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate common weight Combined, (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate , Crotonic acid / formula (I-1) / phenyl (meth) acrylate copolymer, maleic acid / formula (I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / Maleic acid anhydride / formula (I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate common weight Combined, crotonic acid / formula (II-1) / phenyl (meth) acrylate copolymer, maleic acid / formula (II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid Anhydrous / formula (I I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / Formula (I-1) / diethyl maleate copolymer, (meth) acrylic acid / formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate copolymer, crotonic acid / formula (I-1) / diethyl maleate copolymer, maleic acid / formula (I-1) / diethyl maleate copolymer, Copolymer of (meth) acrylic acid / maleic acid 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) / diethyl maleate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / diethyl maleate copolymer, (meth) acrylic acid / formula ( I-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / A copolymer of formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, a copolymer of crotonic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, Maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / formula (II-1) / 2-hydroxyethyl (Meta) acrylate copolymer, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / 2-Hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (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, (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, 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 acid anhydride / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) ) Acrylic acid / bicyclo [2.2.1] hept-2-ene copolymer, crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, malein Acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / maleic acid 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, (Meta) acrylic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / Formula (I-1) / formula (II-1) / N-cyclohexylmaleimide copolymer, crotonic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, maleic acid / formula (I-1) ) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / formula (I-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide copolymer, crotonic acid / formula (II-1) / N-cyclohexylmaleimide copolymer, maleic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexyl maleimide copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-Cyclohexyl maleimide copolymer, (meth) acrylic acid / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (II-1) / styrene copolymer, (me T) Acrylic acid / formula (I-1) / formula (II-1) / styrene copolymer, crotonic acid / formula (I-1) / styrene copolymer, maleic acid / formula (I-1) / Polystyrene copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Polystyrene copolymer, crotonic acid / formula (II-1) / styrene copolymer, maleic acid / formula (II-1) / styrene copolymer, (meth) acrylic acid / maleic acid 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 acid / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / formula (I-1) / formula ( II-1) / N-cyclohexylmaleimide / styrene copolymer, crotonic acid / formula (I-1) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / formula (I-1) / N-cyclohexyl Maleimide / styrene copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula (I-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer, crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / formula (II-1) / N- Cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / formula (II-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer and the like.

The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. , Particularly preferably 5,000 to 10,000. When the weight average molecular weight of the resin (A) is within the above range, the coatability of the curable resin composition tends to be good.
The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is in the above range, the obtained cured film tends to have excellent 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 or less. / 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 required to neutralize 1 g of the polymer, and can be determined by titrating with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the substrate.

The content of the resin (A) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, based on the solid content of the curable resin composition of the present invention. When the content of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the substrate and chemical resistance. Here, the solid content of the curable resin composition means an amount obtained by removing the solvent (E) from the total amount of the curable resin composition of the present 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 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. Examples include type epoxy resins.

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 glycidyl ester type epoxy resin derived from the aromatic carboxylic acid of 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. The glycidyl ether type epoxy resin is more preferable, and the bisphenol A type epoxy resin is further preferable.

The glycidyl ether type epoxy resin can be synthesized by condensing the corresponding phenols and epichlorohydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by a method conventionally known to those skilled in the art.
Moreover, you may use a commercially available product.
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 Toto Kasei Co., Ltd.).
Commercially available phenol novolac type epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), and DEN-438 (manufactured by Dow Chemical Corporation). ) Etc. can be mentioned.
Examples of commercially available o-cresol novolac type epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available polyphenol type epoxy resins include Epicoat 1032H60 and Epicoat YX-4000 (manufactured by Mitsubishi Chemical Corporation).

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, and more preferably 150 to 400 g / eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. Epoxy equivalents can be measured, for example, by the method specified 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.
The weight average molecular weight of the epoxy resin is preferably 300 to 10,000, more preferably 400 to 6,000, and even more preferably 500 to 4,800.

The content of the epoxy resin is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total content of the resin (A) and the epoxy resin (B). When the content of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the 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. Is. When the total content is in the above range, the obtained cured film tends to have excellent 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 polyvalent carboxylic acid anhydride and polyvalent carboxylic acid (hereinafter, may be referred to as "Compound (C)"). May be good.
The polyvalent carboxylic acid (C) is at least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of the 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 acid anhydride, 2-dodecylsuccinic anhydride, 2- (2 octa-3-). Enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarbaryl anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, etc. Chain polyvalent carboxylic acid anhydride;
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] Hepta-5-ene-2,3-dicarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride An alicyclic polyvalent carboxylic acid anhydride such as an anhydride;
Phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid dianhydride, 3,3'4,4'-diphenylsulfonetetra Organic Acid Dianhydride, Ethylene Glycolbis (Anhydrotrimeritate), Glycerintris (Anhydrotrimeritate), Glycerinbis (Anhydrotrimeritate) Monoacetate, 1,3,3a,4,5,9b -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione and other aromatic polyvalent carboxylic acid anhydrides; and the like.
Adeka Hardener-EH-700 (trade name (same below), manufactured by ADEKA Corporation), Ricacid-HH, same-TH, same-MH, same MH-700 (made by New Japan Chemical Co., Ltd.), Epikinia 126, same Commercially available 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 chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids that lead to chain polyvalent carboxylic acid anhydrides. acid;
Cyclohexanedicarboxylic acid, alicyclic polyvalent carboxylic acid An alicyclic polyvalent carboxylic acid such as a polyvalent carboxylic acid that leads to an anhydride;
Examples thereof include isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, aromatic polyvalent carboxylic acid such as polyvalent carboxylic acid which leads to aromatic polyvalent carboxylic acid anhydride; and the like.

Of these, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalent carboxylic acids are preferable because the cured film has excellent heat resistance and the transparency in the visible light region is unlikely to decrease. Acid anhydrides are more preferred.

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

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

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 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-methylphenol), 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 "-(mesitylen-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] dioxaphosfepine and the like Can be mentioned.
As the phenolic antioxidant, a commercially available product may be used. Examples of commercially available phenolic antioxidants include Sumilyzer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, etc. Examples thereof include 3114 (all manufactured by BASF) and the like.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, disstearyl 3,3'-thiodipropionate, and pentaerythrityl tetrakis (3-lauryl). Thiopropionate) and the like. As the sulfur-based antioxidant, a commercially available product may be used. Examples of commercially available sulfur-based antioxidants include Sumilyzer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-. Examples thereof include tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite and the like. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos (registered trademark) 168, 12, 38 (all manufactured by BASF), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). ..

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

The content of the antioxidant (D) is 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the resin (A). When the content of the antioxidant (D) is within the above range, the obtained cured film tends to be excellent in heat resistance and pencil hardness.

The curable resin composition of the present invention is a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter, may be referred to as "(meth) acrylic compound (F)"). May include.

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

Examples of the (meth) acrylic compound (F) having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di. (Meta) 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 di (meth) acrylate, 3-methylpentane Examples thereof include diol di (meth) acrylate.

Examples of the (meth) acrylic compound (F) having three or more (meth) acryloyl groups include trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth). ) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Propoxylated Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate , Tripenta erythritol tetra (meth) acrylate, tripenta erythritol penta (meth) acrylate, tripenta erythritol hexa (meth) acrylate, tripenta erythritol hepta (meth) acrylate, tripenta erythritol octa (meth) acrylate, pentaerythritol tri ( Reaction product of meta) 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 trimethylol Propanetri (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 (Meta) acrylate, caprolactone-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, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate Reactions with acid anhydrides, caprolactone-modified tripentaerythritol hepta (meth) acrylates and acid anhydrides Reactants and the like can be mentioned.
As the (meth) acrylic compound (F), a (meth) acrylic compound (F) having three or more (meth) acrylic loyl 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, and more preferably 25 to 70 parts by mass with respect to 100 parts by mass of the resin (A). When the content of the (meth) acrylic compound (F) is within the above range, the chemical resistance and mechanical strength of the obtained cured film tend to be good.

<Solvent (E)>
The 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-), and an ether ester. Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent And dimethylsulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene 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, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, and methyl anisole.

Examples of the ether ester solvent 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

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. And so on.

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

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 solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. Of 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.

The content of the solvent (E) is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total amount of the curable resin composition of the present invention. 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. When 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 a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 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 LLC) Made) and the like.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain.
Specifically, Fluorinert (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, R30 (DIC) EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Corporation), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation). Preferred is Mega Fvck® F475.

The surfactant (G) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass, based on the total amount of the curable resin composition of the present invention. Hereinafter, it is more preferably 0.01% by mass or more and 0.05% by mass or less. By containing a surfactant in this range, the flatness of the cured film can be improved.

<Other ingredients>
If necessary, 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 accelerator.

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

Specific examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile).
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene and the like.
Adhesion promoters include 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-isocyanoxidetriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

The curable resin composition of the present invention does not substantially contain a photopolymerization initiator. That is, in the curable resin composition of the present invention, the content of the photopolymerization initiator in the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass, and more preferably less than 0.1% by mass. Is. Examples of the photopolymerization initiator include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and oxime compounds.

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

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

In the cured film made of the curable resin composition of the present invention, the average transmittance of the cured film is preferably 80% or more, 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 for 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 the average value when measured below. This makes it possible to provide a cured film having excellent transparency in the visible light region.

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

<Method for producing a cured film of the present invention>
The cured film made of the curable resin composition of the present invention is obtained by applying the curable resin composition of the present invention on a substrate and curing it by heat.
Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed on the substrate.
The coating on the substrate is preferably performed using various coating devices such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

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

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

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are 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, 230 parts of propylene glycol monomethyl ether acetate was added, and the mixture was 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 ] deca-8 and 9-ylacrylate, and 85 parts of propylene glycol monomethyl ether acetate was added. It was added dropwise 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 the dropping, the mixture was kept at the same temperature for 4 hours, cooled to room temperature, and 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 weight average molecular weight (Mw) of the produced resin Aa was 7200, and the dispersity was 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, 224 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, 42 parts of acrylic acid, 21 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8 and 9-ylacrylate, 147 parts of cyclohexylmaleimide, and 445 parts of propylene glycol monomethyl ether acetate. The mixed solution of the part was added dropwise over 4 hours.
On the other hand, a mixed solution prepared by dissolving 10 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 111 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping, the copolymer was kept at the same temperature for 4 hours, cooled to room temperature, and had a B-type viscosity (23 ° C.) of 18 mPas, a solid content of 22.9% by mass, and a solution acid value of 20 mg-KOH / g (resin). Ab) was obtained. The produced resin Ab had a weight average molecular weight of 11200 and a dispersity of 2.1.

<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, 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 ] deca-8 and 9-ylacrylate, 78 parts of phenylmaleimide, 140 parts of propylene glycol monomethyl ether acetate. The mixed solution of parts was added dropwise over 5 hours.
On the other hand, 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 the dropping, the mixture was kept at the same temperature for 3 hours, cooled to room temperature, and 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 of 9400 and a dispersity of 2.2.

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

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

In Table 1, the resin content represents a mass portion in terms of solid content.
Resin (Aa): Resin obtained in Synthesis Example 1 Resin (Ab): Resin obtained in Synthesis Example 2 Resin (Ac): Resin obtained in Synthesis Example 3 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 (oxylanylmethyl) aniline] (manufactured by SYNASIA)
Compound (X): Monoallyl diglycidyl isocyanuric acid (MA-DGIC: manufactured by Shikoku Chemicals Corporation)
Polycarboxylic acid (C): 1,2,3,6-tetrahydrophthalic anhydride (Ricacid TH; manufactured by New Japan Chemical 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) ) -Trion (IRGANOX® 3114; manufactured by BASF)
Surfactant (H); Megafuck (registered trademark) F554 (manufactured by DIC Corporation)
Solvent (E): Ea: Propylene glycol monomethyl ether acetate The solvent (E) was mixed so that the solid content of the curable resin composition was "solid content (%)" in Table 1.

<Preparation of cured film>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and isopropanol, and then dried. The curable resin composition was spin-coated on this glass substrate so that the film thickness after post-baking was 1.5 μm, and then prebaked at 100 ° C. for 3 minutes in a clean oven. Then, it was post-baked 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.) at 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. The adhesion of the cured film to the glass substrate was evaluated by the 8.5.3 adhesive grid tape method of −1990. Table 2 shows the number of grids in which 95% or more of the cured film is clearly left on the substrate out of 100 grids as the adhesion (pieces).

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

Claims (8)

Structural units derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
A resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond.
Alicyclic polyvalent carboxylic acid anhydride, and
Look containing a compound having a group represented by the formula (1),
A curable resin composition in which the content of the alicyclic polyvalent carboxylic acid anhydride is 2 to 70 parts by mass with respect to 100 parts by mass of the resin.

[In the 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 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 the formula (1) is a compound represented by the formula (2).

[In the formula (2), R ¹ and R ² have the same meanings as described above.
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an oxacycloalkyl alkyl group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and the oxa. The -CH _2- contained in the cycloalkylalkyl group and the aralkyl group may be replaced with -O- or -S-. ] The curable resin composition according to claim 3, wherein R ³ is a group having at least one epoxy structural group. The curable resin composition according to any one of claims 1 to 4, further comprising a compound having an epoxy group (however, different from the compound having a group represented by the formula (1)). Structural units derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
A resin containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond
The curable resin composition according to any one of claims 1 to 5, which is a resin containing a structural unit derived from a monomer having a maleimide structure. Do that hardening film from the curable resin composition according to any one of claims 1 to 6. A display device including the cured film according to claim 7.