TWI579330B - Curable resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition.

In the liquid crystal display device, a cured film such as a photo spacer or an overcoat is formed using a curable resin composition. In the case of such a curable resin composition, copolymerization of methacrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate and methacrylic acid containing only an epoxy equivalent of 500 g/eq or less is known. Composition of matter (JP2010-202842-A).

However, when the cured resin composition proposed in the prior art forms a cured film on a substrate having a height difference, the height difference cannot be completely eliminated. Therefore, the flatness of the obtained cured film may not be completely satisfactory.

The present invention encompasses the following inventions.

[1] A curable resin composition comprising a resin (A) and a resin (B), and a content ratio of the resin (A) to the resin (B) is 40:60 to 90:10 on a mass basis. By; The resin (A) contains a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. The structural unit of the monomer, and the epoxy equivalent is 200 g/eq or more and 500 g/eq or less; the resin (B) contains a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. And a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and having an epoxy equivalent of 1200 g/eq or more and 2600 g/eq or less.

[2] The curable resin composition according to [1], which further contains an antioxidant.

[3] The curable resin composition according to [1] or [2], which further contains a solvent.

[4] A cured film formed of the curable resin composition according to any one of [1] to [3].

[5] A display device comprising the cured film according to [4].

According to the curable resin composition of the present invention, a cured film excellent in flatness can be produced.

In the present specification, the compounds exemplified for the respective components may be used singly or in combination of plural kinds unless otherwise specified.

The curable resin composition of the present invention comprises a resin (A) and resin (B).

The resin (A) contains a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. a structural unit of a monomer having an epoxy equivalent of 200 g/eq or more and 500 g/eq or less; The resin (B) contains a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. The structural unit of the monomer, and the epoxy equivalent is 1200 g/eq or more and 2600 g/eq or less.

The curable resin composition of the present invention is preferably one containing the solvent (E), the antioxidant (F), and/or the surfactant (H).

Further, the curable resin composition of the present invention comprises at least one selected from the group consisting of: a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin. An epoxy resin (hereinafter referred to as "epoxy resin (C)") and/or a compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids (hereinafter referred to as "polycarboxylic acid" The case of acid (G) is preferred.

<Resin>

The resin used in the curable resin composition of the present invention is a copolymer comprising at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(a) The structural unit of the case and the structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as "(b)"). The copolymer may further have a copolymerizable from (a) and (a) And (b) is a structural unit of a different monomer (hereinafter referred to as "(c)").

The resin is preferably the following resin "K1" and resin "K2".

Resin "K1": a copolymer of (a) and (b); and a resin "K2": a copolymer of (a) and (b) and (c).

Specific examples of (a) include acrylic acid, methacrylic acid, crotonic acid, unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid; maleic acid and fumaric acid; , citraconic acid, mesaconic acid, isaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6 - unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyl tetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2 - alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-B Carboxyl-containing bicyclic unsaturated compounds such as heptane [2.2.1] hept-2-ene; maleic anhydride, citraconic anhydride, isaconic anhydride, 3-vinyl phthalic anhydride, 4-vinylbenzene Dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydration 5,6- Unsaturated dicarboxylic anhydrides such as dicarboxybicyclo[2.2.1]hept-2-ene; succinic acid [2-(Methyl)propenyloxyethyl]ester and an unsaturated monocarboxylic acid of a divalent or higher polycarboxylic acid such as mono-2-[methyl)propenyloxyethyl]ester Alkyl oxyalkylene esters; For example, an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)acrylate.

Among these, (meth)acrylic acid, maleic anhydride, etc. are preferable, and (meth)acrylic acid is more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution.

In the present specification, the term "(meth)acryloyl group" means at least one selected from the group consisting of an acryloyl group and a methacryl group. The expressions "(meth)acrylic acid" and "(meth) acrylate" have the same meaning.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethyl group A polymerizable compound having a saturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

(b) Examples thereof include a monomer having an oxiranyl group and an ethylenically unsaturated bond (b1) (hereinafter referred to as "(b1)"), and having an oxetane a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) (hereinafter referred to as "(b3)"), etc.

(b1), for example, a monomer (b1-1) having a structure in which an aliphatic unsaturated hydrocarbon having a linear or branched chain is epoxidized (hereinafter referred to as "(b1-1)" In the case of the monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-2)").

Examples of (b1-1) include, for example, glycidyl methacrylate, (meth)acrylic acid-β-methylglycidylpropyl ester, and (meth)acrylic acid-β-B. Glycidyl propyl ester, propylene propyl vinyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinyl benzyl epoxy propyl ether, α -methyl-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl-p-vinylbenzyloxypropyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene , 2,6-bis(glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-paran (glycidoxy) Methyl)styrene, 2,3,6-glycol (glycidoxymethyl)styrene, 3,4,5-glycol (glycidoxymethyl)styrene, 2,4,6- Ginseng (glycidoxymethyl) styrene and the like.

Examples of (b1-2) include vinylcyclohexene monoxide and 1,2-epoxy-4-vinylcyclohexene (e.g., Celloxide 2000; manufactured by Daicel Co., Ltd.). , (meth)acrylic acid-3,4-epoxycyclohexyl methyl ester (such as: Cyclomer A400; manufactured by Daicel Co., Ltd.), (meth)acrylic acid-3,4-epoxycyclohexyl methyl ester (such as: Cyclomer) M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the general formula (I) and the general formula (II), R ^b1 and R ^{b2 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. .

X ^b1 represents a single bond and X ^{b2 system, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* is a bond with O.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and t-butyl groups.

The alkyl group in which the hydrogen atom is a hydroxyl group may, for example, be a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group or a 3-hydroxypropyl group. - hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^b1 and R ^{b2 are} preferably, for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

The alkanediyl group may, for example, be a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1. 5-diyl, hexane-1,6-diyl and the like.

X ^b1 and X ^{b2 are} preferably exemplified by a single bond, a methylene group, an ethylidene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably, for example, a single The bond, *-CH ₂ CH ₂ -O- (* indicates the bond group with O).

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formula (I-1) to the formula (I-15). Among them, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), A compound of the formula (I-9) or the formula (I-11) to the formula (I-15) is preferred, and the formula (I-1), the formula (I-7), and the formula (I) The compound represented by the formula I-9) or the formula (I-15) is more preferably.

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formula (II-1) to the formula (II-15). Among them, the general formula (II-1), the general formula (II-3), the general formula (II-5), the general formula (II-7), the general formula (II-9) or the general formula (II-11) The compound represented by the formula (II-15) is preferably a compound of the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15). The compound is more preferred.

The compound represented by the formula (I) and the compound of the formula (II) may be used alone or in combination of two or more. When the compound of the formula (I) and the compound of the formula (II) are used in combination, the ratio of the compound (the compound represented by the formula (I): the compound of the formula (II)] is The molar reference meter is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

(b2) It is preferred to use a monomer having an oxetane group and a (meth) acryloxy group. (b2) may, for example, be 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3 Ethyl-3-propenyloxyethyloxetane and the like.

(b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofuran acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Co., Ltd.), and tetrahydrofuran methacrylate.

(b) is preferable as point (b) in that the reliability of the obtained cured film is improved in heat resistance and chemical resistance. Further, it is preferable that (b1-2) is preferable in terms of excellent storage stability of the curable resin composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, and (meth)acrylic acid. Third butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-ester (in this In the technical field, the conventional name is "dicyclopentanyl methacrylate", and there is also a case called "tricyclodecyl (meth) acrylate), trimethyl (meth) acrylate [ 5.2.1.0 ^2,6 ]decene-8-ester (in the technical field, the commonly used name is "dicyclopentenyl methacrylate"), dicyclopentyl (meth)acrylate Ethyl ethyl ester, isodecyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (A) Naphthyl acrylate, benzene (meth) acrylate (meth) acrylates such as esters; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; maleic acid a dicarboxylic acid diester such as diethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane- 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- Alkene, 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-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[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 - alkene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6- Bis(cyclobutoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimide-3-cis Acetylimine benzoate, N-succinimide-4-butyleneimine butyrate, N-succinimide-6-m-butyleneimine caproate a dicarbonyl quinone imine derivative such as an ester, N-succinimide-3-oxanediimide propionate or N-(9-acridinyl) maleimide; benzene Ethylene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene (vinylidene chlorid), acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene Wait.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, and N are used. -Benzylmethyleneimineimine and bicyclo[2.2.1]hept-2-ene are preferred.

Specific examples of the resin [K1] include a compound represented by (meth)acrylic acid/general formula (I-1) (hereinafter abbreviated as "general formula (I-1)". -2) Others are the same) copolymers, (methyl) Acrylic acid / copolymer of the formula (I-2), (meth)acrylic acid / copolymer of the formula (I-3), (meth)acrylic acid / copolymer of the formula (I-4), (methyl Acrylic acid / copolymer of the formula (I-5), (meth)acrylic acid / copolymer of the formula (I-6), (meth)acrylic acid / copolymer of the formula (I-7), (A) Acrylic acid / copolymer of the formula (I-8), (meth)acrylic acid / copolymer of the formula (I-9), (meth)acrylic acid / copolymer of the formula (I-10), Methyl)acrylic acid / copolymer of the formula (I-11), (meth)acrylic acid / copolymer of the formula (I-12), (meth)acrylic acid / copolymer of the formula (I-13), (Meth)acrylic acid / copolymer of the formula (I-14), (meth)acrylic acid / copolymer of the formula (I-15), (meth)acrylic acid / copolymer of the formula (II-1) , (meth)acrylic acid / copolymer of the formula (II-2), (meth)acrylic acid / copolymer of the formula (II-3), copolymerization of (meth)acrylic acid / general formula (II-4) , (meth)acrylic acid / copolymer of the formula (II-5), (meth)acrylic acid / copolymer of the formula (II-6), (meth)acrylic acid / formula (II-7) Copolymer, (meth)acrylic acid / copolymer of formula (II-8), (meth)acrylic acid / Copolymer of the formula (II-9), (meth)acrylic acid / copolymer of the formula (II-10), (meth)acrylic acid / copolymer of the formula (II-11), (meth)acrylic acid / copolymer of the formula (II-12), (meth)acrylic acid / copolymer of the formula (II-13), (meth)acrylic acid / copolymer of the formula (II-14), (methyl) Acrylic acid / copolymer of the formula (II-15), (meth)acrylic acid / copolymer of the formula (I-1) / formula (II-1), (meth)acrylic acid / formula (I-2) / copolymer of the formula (II-2), (meth)acrylic acid / copolymer of the formula (I-3) / formula (II-3), (meth)acrylic acid / formula (I-4) / copolymer of the formula (II-4), (meth)acrylic acid / copolymer of the formula (I-5) / formula (II-5), (meth)acrylic acid / formula (I-6) ) / copolymer of the formula (II-6), (meth)acrylic acid / copolymer of the formula (I-7) / formula (II-7), (meth)acrylic acid / formula (I-8) / copolymer of the formula (II-8), (meth)acrylic acid / copolymer of the formula (I-9) / formula (II-9), (meth)acrylic acid / formula (I-10) / copolymer of the formula (II-10), (meth)acrylic acid / copolymer of the formula (I-11) / formula (II-11), (meth)acrylic acid / formula (I-12) / copolymer of the formula (II-12), (meth)acrylic acid / copolymer of the formula (I-13) / formula (II-13), (meth)acrylic acid / formula (I-14) / copolymer of the formula (II-14), (meth)acrylic acid / copolymer of the formula (I-15) / formula (II-15), (meth)acrylic acid / formula (I-1) / copolymer of the formula (I-7), (meth)acrylic acid / copolymer of the formula (I-1) / formula (II-7), crotonic acid / copolymer of the formula (I-1) , Crotonic acid / copolymer of the formula (I-2), crotonic acid / copolymer of the formula (I-3), crotonic acid / copolymer of the formula (I-4), crotonic acid / formula (I -5) copolymer, crotonic acid / copolymer of the formula (I-6), crotonic acid / copolymer of the formula (I-7), crotonic acid / copolymer of the formula (I-8), croton Acid / copolymer of formula (I-9) Crotonic acid / copolymer of the formula (I-10), crotonic acid / copolymer of the formula (I-11), crotonic acid / copolymer of the formula (I-12), crotonic acid / formula (I- 13) copolymer, crotonic acid / copolymer of the formula (I-14), crotonic acid / copolymer of the formula (I-15), crotonic acid / copolymer of the formula (II-1), crotonic acid / copolymer of the formula (II-2), crotonic acid / copolymer of the formula (II-3), crotonic acid / copolymer of the formula (II-4), crotonic acid / formula (II-5) Copolymer, crotonic acid / copolymer of formula (II-6), crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / pass Copolymer of formula (II-9), crotonic acid / copolymer of formula (II-10), crotonic acid / general formula Copolymer of (II-11), crotonic acid / copolymer of the formula (II-12), crotonic acid / copolymer of the formula (II-13), crotonic acid / copolymer of the formula (II-14) , Crotonic acid / copolymer of the formula (II-15), maleic acid / copolymer of the formula (I-1), maleic acid / copolymer of the formula (I-2), cis Butene acid / copolymer of the formula (I-3), maleic acid / copolymer of the formula (I-4), maleic acid / copolymer of the formula (I-5), Maleic acid / copolymer of the formula (I-6), maleic acid / copolymer of the formula (I-7), maleic acid / copolymer of the formula (I-8) , copolymer of maleic acid / formula (I-9), copolymer of maleic acid / formula (I-10), copolymer of maleic acid / formula (I-11) , maleic acid / copolymer of formula (I-12), maleic acid / copolymer of formula (I-13), maleic acid / formula (I-14) Copolymer, maleic acid / copolymer of the formula (I-15), maleic acid / copolymer of the formula (II-1), maleic acid / formula (II-2) Copolymer, maleic acid / copolymer of formula (II-3), maleic acid / copolymer of formula (II-4), butene Diacid / copolymer of the formula (II-5), maleic acid / copolymer of the formula (II-6), maleic acid / copolymer of the formula (II-7), cis Etheric acid / copolymer of the formula (II-8), maleic acid / copolymer of the formula (II-9), maleic acid / copolymer of the formula (II-10), cis Butic acid/copolymer of the formula (II-11), maleic acid/copolymer of the formula (II-12), maleic acid/copolymer of the formula (II-13), Maleic acid / copolymer of the formula (II-14), maleic acid / copolymer of the formula (II-15), (meth)acrylic acid / maleic anhydride / formula (I -1) copolymer, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-2), (meth)acrylic acid / maleene Diacid anhydride / copolymer of the formula (I-3), (meth)acrylic acid / maleic anhydride / copolymer of the formula (I-4), (meth)acrylic acid / maleic anhydride / pass Copolymer of the formula (I-5), (meth)acrylic acid/maleic anhydride/copolymer of the formula (I-6), (meth)acrylic acid/maleic anhydride/formula (I- 7) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-9) , (meth)acrylic acid/maleic anhydride/copolymer of formula (I-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-11), (a) Acrylic acid/maleic anhydride/copolymer of the formula (I-12), (meth)acrylic acid/maleic anhydride/copolymer of the formula (I-13), (meth)acrylic acid/ Maleic anhydride / copolymer of the formula (I-14), (meth)acrylic acid / maleic anhydride / copolymer of the formula (I-15), (meth)acrylic acid / maleic acid Anhydride / copolymer of the formula (II-1), (meth)acrylic acid / maleic anhydride / copolymer of the formula (II-2), (meth)acrylic acid / maleic anhydride / general formula (II-3) copolymer, (methyl Acrylic acid/maleic anhydride/copolymer of the formula (II-4), (meth)acrylic acid/maleic anhydride/copolymer of the formula (II-5), (meth)acrylic acid/cis Butic anhydride/copolymer of formula (II-6), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-7), (meth)acrylic acid/maleic anhydride / copolymer of the formula (II-8), (meth)acrylic acid / maleic anhydride / copolymer of the formula (II-9), (meth)acrylic acid / maleic anhydride / formula ( Copolymer of II-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-11), (meth)acrylic acid/maleic anhydride/formula (II-12) Copolymer, (meth)acrylic acid / maleic anhydride / general formula (II-13) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-14), (meth)acrylic acid/maleic anhydride/formula (II-15) Copolymer, etc.

Specific examples of the resin [K2] include (meth)acrylic acid/copolymer of the formula (I-1)/methyl (meth)acrylate, and (meth)acrylic acid/formula (I-2) /(Methyl) acrylate copolymer, (meth)acrylic acid / copolymer of the formula (I-3) / methyl (meth) acrylate, (meth) acrylic / formula (I-4) /(Methyl) acrylate copolymer, (meth)acrylic acid / copolymer of the formula (I-5) / methyl (meth) acrylate, (meth) acrylic / formula (I-6) Copolymer of methyl (meth) acrylate, copolymer of (meth)acrylic acid / methyl (I-7) / methyl (meth) acrylate, (meth) acrylic / formula (I-8) Copolymer of methyl (meth) acrylate, copolymer of (meth)acrylic acid / methyl (I-9) / methyl (meth) acrylate, (meth) acrylic / formula (I-10) Copolymer of methyl (meth) acrylate, copolymer of (meth)acrylic acid / methyl (I-11) / methyl (meth) acrylate, (meth) acrylic / formula (I-12) Copolymer of methyl (meth) acrylate, copolymer of (meth)acrylic acid / methyl (I-13) / methyl (meth) acrylate, (meth) acrylic / formula (I-14) /(Methyl) acrylate copolymer, (A Acrylic acid / copolymer of the formula (I-15) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-1) / methyl (meth) acrylate, (methyl Acrylic acid / copolymer of the formula (II-2) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-3) / methyl (meth) acrylate, (methyl Acrylic acid / copolymer of the formula (II-4) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-5) / methyl (meth) acrylate, (methyl )acrylic acid/ Copolymer of the formula (II-6) / methyl (meth)acrylate, (meth)acrylic acid / copolymer of the formula (II-7) / methyl (meth)acrylate, (meth)acrylic acid / Copolymer of the formula (II-8) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-9) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of the formula (II-10)/methyl (meth) acrylate, (meth)acrylic acid / copolymer of the formula (II-11) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of the formula (II-12) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of the formula (II-14) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-15) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of the formula (I-1)/dicyclopentanyl (meth)acrylate, (meth)acrylic acid / copolymer of the formula (II-1) / dicyclopentanyl (meth)acrylate, (A) Acrylic acid / copolymer of the formula (I-1) / formula (II-1) / (meth)acrylic acid dicyclopentyl ester, crotonic acid / general formula (I-1) / (meth) acrylic acid Copolymer of cyclopentyl ester, cis-butane Diacid / copolymer of formula (I-1) / dicyclopentanyl (meth)acrylate, (meth)acrylic acid / maleic anhydride / formula (I-1) / (meth)acrylic acid Copolymer of cyclopentyl ester, (meth)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / dicyclopentyl (meth) acrylate, crotonic acid / formula (II- 1) / Copolymer of dicyclopentanyl (meth)acrylate, copolymer of maleic acid / dicyclopentanyl (I-1) / (meth) acrylate, (meth) acrylic / cis Butic anhydride/copolymer of formula (II-1)/dicyclopentanyl (meth)acrylate, (meth)acrylic acid/formula (II-1)/methyl (meth)acrylate/(A) Copolymer of dicyclopentyl acrylate, (meth)acrylic acid / copolymer of phenyl (I-1) / phenyl (meth) acrylate, (meth) acrylic / formula (II-1) Copolymer of /(meth)acrylic acid acrylate, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / general formula Copolymer of (I-1)/phenyl (meth)acrylate, copolymer of maleic acid/formula (I-1)/phenyl (meth)acrylate, (meth)acrylic acid/cis. Adipic anhydride / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / (meth) acrylate Copolymer of phenyl ester, crotonic acid / copolymer of formula (II-1) / phenyl (meth) acrylate, maleic acid / phenyl formula (II-1) / (meth) acrylate Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/phenyl (meth)acrylate, (meth)acrylic acid/formula (II-1)/(A) Copolymer of methyl acrylate/phenyl (meth) acrylate, (meth)acrylic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / pass Copolymer of the formula (II-1) / diethyl maleate, (meth)acrylic acid / general formula (I-1) / general formula (II-1) / diethyl maleate Copolymer, crotonic acid / general formula (I-1) / maleic acid Copolymer of ethyl ester, maleic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / maleic anhydride / formula (I-1 / copolymer of diethyl maleate, (meth)acrylic acid / copolymer of the formula (I-1) / methyl (meth) acrylate / diethyl maleate, crotonic acid / copolymer of the formula (II-1) / diethyl maleate, copolymer of maleic acid / formula (II-1) / diethyl maleate, (methyl Acrylic acid/maleic anhydride/copolymer of the formula (II-1)/diethyl maleate, (meth)acrylic acid/methyl (I-(1))/(meth)acrylate / copolymer of diethyl maleate, (meth)acrylic acid / copolymer of formula (I-1) / (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid / general formula (II-1) /(Methyl methacrylate) copolymer, (meth)acrylic acid / general formula (I-1) / general formula (II-1) / (meth)acrylic acid 2-hydroxyethyl ester Copolymer, crotonic acid / copolymer of formula (I-1) / 2-hydroxyethyl (meth)acrylate, maleic acid / formula (I-1) / (meth)acrylic acid-2 Copolymer of -hydroxyethyl ester, (meth)acrylic acid/maleic anhydride / copolymer of formula (I-1) / (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid / pass Copolymer of the formula (I-1) / methyl (meth)acrylate / 2-hydroxyethyl (meth)acrylate, crotonic acid / hydroxy group of the formula (II-1) / (meth) acrylate Copolymer of ethyl ester, maleic acid / copolymer of formula (II-1) / 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / maleic anhydride / formula ( II-1)/Copolymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / Methyl Formula (II-1) / Methyl (meth)acrylate / (Meth)acrylic acid-2- Copolymer of hydroxyethyl ester, (meth)acrylic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (II-1) / Bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid / general formula (I-1) / pass (II-1)/bicyclo[2.2.1]Hept-2-ene copolymer, crotonic acid/copolymer of formula (I-1)/bicyclo[2.2.1]hept-2-ene, maleene Diacid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / maleic anhydride / formula (I-1) / bicyclo [2.2. 1] copolymer of hept-2-ene, (meth)acrylic acid / copolymer of the formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, crotonic acid / copolymer of the formula (II-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/bicyclo[2.2.1]hept-2-ene, (meth)acrylic acid/formula (II-1) /(Methyl) methacrylate / bicyclo [2.2.1] hept-2-ene copolymer, (methyl) propyl Acrylic acid / copolymer of the general formula (I-1) / N-cyclohexyl maleimide, (meth)acrylic acid / general formula (II-1) / N-cyclohexyl maleic acid Copolymer of amine, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / N-cyclohexyl maleimide, crotonic acid / formula (I- 1) a copolymer of /N-cyclohexylmethyleneimine, a copolymer of maleic acid / general formula (I-1) / N-cyclohexyl maleimide, (methyl Acrylic acid/maleic anhydride/copolymer of the formula (I-1)/N-cyclohexylmethyleneimine, (meth)acrylic acid / general formula (I-1) / (methyl) Copolymer of methyl acrylate/N-cyclohexylmethylene iodide, crotonic acid / copolymer of the formula (II-1) / N-cyclohexyl maleimide, maleic acid /Copolymer of the general formula (II-1)/N-cyclohexylmethyleneimine, (meth)acrylic acid/maleic anhydride/formula (II-1)/N-cyclohexyl cis-butane Copolymer of enediamine, (meth)acrylic acid / copolymer of the formula (II-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, (meth) Acrylic / copolymer of formula (I-1) / styrene, (meth)acrylic acid / Copolymer of formula (II-1)/styrene, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / styrene, crotonic acid / formula (I-1 / styrene copolymer, maleic acid / copolymer of the formula (I-1) / styrene, (meth)acrylic acid / maleic anhydride / general formula (I-1) / styrene Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / styrene, crotonic acid / copolymer of formula (II-1) / styrene, cis Butic acid/copolymer of formula (II-1)/styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/styrene, (meth)acrylic acid /Copolymer of the general formula (II-1) / methyl (meth) acrylate / styrene, (meth) acrylic acid / general formula (I-1) / N-cyclohexyl maleic acid Amine/styrene copolymer, (meth)acrylic acid / copolymer of the formula (II-1) / N-cyclohexylmethylene iminoimide / styrene, (meth)acrylic acid / general formula (I -1) / copolymer of the formula (II-1) / N-cyclohexyl maleimide / styrene, crotonic acid / general formula (I-1) / N-cyclohexyl maleic acid Copolymer of imine/styrene, copolymer of maleic acid / formula (I-1) / N-cyclohexylmethylene iodide / styrene, (meth)acrylic acid / maleic acid Diacid anhydride / copolymer of the formula (I-1) / N-cyclohexyl maleimide / styrene, (meth) acrylic acid / methyl (I-1) / (meth) acrylate /N-cyclohexylmethyleneimine / styrene copolymer, crotonic acid / copolymer of the formula (II-1) / N-cyclohexyl maleimide / styrene, cis Alkenedioic acid / copolymer of the general formula (II-1) / N-cyclohexyl maleimide / styrene, (meth) acrylic acid / maleic anhydride / general formula (II-1) / Copolymer of N-cyclohexylmethyleneimine/styrene, (meth)acrylic acid / general formula (II-1) / methyl (meth) acrylate / N-cyclohexyl succinimide A copolymer of amine/styrene, and the like.

Such a resin can be produced by a generally known method (for example, a radical polymerization method or the like). The obtained resin can be directly used for preparing the curable resin composition of the present invention, or a solution obtained by concentration or dilution, or a solid (powder) taken by reprecipitation or the like. . In particular, when a solvent used for the curable resin composition of the present invention is used in the production of a resin, the solution after the reaction can be used as it is to produce a curable resin composition, so that the production step of the curable resin composition can be simplified.

Resin (A) is a copolymer of the above, and an epoxy equivalent system 200 g / eq or more and 500 g / eq or less, preferably 220 g / eq or more and 400 g / eq or less.

The epoxy equivalent can be measured, for example, by a method defined by JIS K7236 (preferably, an indicator titration method).

In the case of the resin (A) resin [K1], the ratio of the structural unit derived from each monomer is from 5 to 60 mol% from the structural unit of (a) with respect to the total structural unit constituting the resin (A). The structural unit of (b): preferably 40 to 95 mol%, and the structural unit derived from (a): 10 to 50 mol%. The structural unit derived from (b): 50 to 90 mol% is more preferably.

In the case of the resin (A) resin [K2], the ratio of the structural unit from each of the structural units of the resin (A) is from 2 to 40 mol% from (a) b) Construction unit: 2 to 95 mol% structural unit from (c): preferably 1 to 65 mol%, with structural unit from (a): 5 to 35 mol% from (b) construction Unit: 5 to 80 mol% The structural unit derived from (c): 1 to 60 mol% is more preferable.

In resin (A), the lower the proportion of structural units from (b) The epoxy equivalent of the obtained resin tends to be higher, so that the structural unit derived from (b) can be made in the ratio range of the above structural unit by the resin having a smaller epoxy equivalent at the time of its manufacture. The ratio is increased, and the resin having a larger epoxy equivalent is lowered and the like is appropriately set to obtain a resin having a predetermined epoxy equivalent.

When the ratio of the structural unit of the resin (A) is within the above range, the chemical resistance of the cured film tends to be excellent.

The weight average molecular weight of the resin (A) to polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight of the resin (A) is within the above range, the coating property of the curable resin composition tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the chemical resistance of the obtained cured film tends to be excellent.

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 50 mg-KOH/g or more and 135 mg-KOH. /g is better and below. In the above, the acid value is a measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, 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 adhesion between the cured film and the substrate tends to be excellent.

Resin (B) is a copolymer of the above, and the epoxy equivalent is 1200 g/eq or more and 2600 g/eq or less, preferably 1400 g/eq or more and 2500 g/eq or less.

The epoxy equivalent was determined in the same manner as above.

The resin (B) is preferably a resin [K2]. In this case, the ratio of the structural units from each of the structural units constituting the resin (B) is from the structural unit of (a): 4 to 40 mol% from the structural unit of (b): 1 Up to 10 mol% of the structural unit from (c): 50 to 95 mol% is preferred, with structural units from (a): 8 to 35 mol% from (b) tectonic units: 2 to 9 mo The ear % comes from the structural unit of (c): 56 to 90 mol% is more preferred.

In the resin (B), the lower the ratio of the structural unit derived from (b), the higher the epoxy equivalent of the obtained resin tends to be, so that it can be made to have a smaller epoxy resin at the time of its production. The equivalent resin is appropriately set in the ratio range of the above-mentioned structural unit, and the resin having a predetermined epoxy equivalent is obtained by appropriately increasing the ratio of the structural unit derived from (b) and lowering the resin having a larger epoxy equivalent.

When the ratio of the structural unit of the resin (B) is within the above range, the heat resistance of the obtained cured film tends to be better.

The weight average molecular weight of the resin (B) to polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. It is better from 5,000 to 30,000. When the weight average molecular weight of the resin (B) is within the above range, the coatability 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 (B) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the obtained cured film tends to be excellent in chemical resistance.

The acid value of the resin (B) is preferably 30 mg-KOH/g or more and 220 mg-KOH/g or less, more preferably 40 mg-KOH/g or more and 215 mg-KOH/g or less, and 50 mg-KOH/g or more 210 mg-KOH/ g below is better. In the middle, the acid value refers to a measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution. When the acid value of the resin (B) is within the above range, the adhesion between the cured film and the substrate tends to be excellent.

The curable resin composition of the present invention may contain a resin other than the resin (A) and the resin (B). In this case, the content of the resin other than the resin (A) and the resin (B) is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, based on the total amount of the resin.

The content ratio of the resin (A) to the resin (B) [resin (A): resin (B)] is preferably 40:60 to 90:10 on the mass basis, and more preferably 60:40 to 90:10. .

The total amount of the resin is preferably from 30 to 90% by mass, more preferably from 35 to 80% by mass, still more preferably from 40 to 70% by mass, based on the solid content of the curable resin composition of the present invention. When the total amount of the resin is within the aforementioned range, The obtained cured film tends to be excellent in heat resistance and excellent in adhesion to a substrate and chemical resistance. In the solid content of the curable resin composition, the amount of the solvent (E) is subtracted from the total amount of the curable resin composition of the present invention.

<Epoxy Resin (C)>

The epoxy resin (C) is not particularly limited as long as it has a structure different from that of the resin (A), but is selected from epoxy propylene ether type epoxy resins and epoxy propyl ester type epoxy resins. At least one of the groups of resins is preferred.

The epoxy propyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, which can be synthesized by reacting a phenol or a polyhydric alcohol with epichlorohydrin.

Specific examples of the epoxy propyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and phenol novolac type epoxy resin. , o-cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, and the like.

The epoxy propyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure, and can be synthesized by reacting a carbonyl group such as a phthalic acid derivative or a fatty acid with epichlorohydrin.

Examples of the epoxy propyl ester type epoxy resin include a epoxy propyl ester type epoxy resin derived from an aromatic carboxylic acid such as p-oxybenzoic acid, m-oxybenzoic acid or terephthalic acid.

The epoxy resin (C) used in the curable resin composition of the present invention is preferably an aromatic epoxy resin, and is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolak type ring. Oxygen resin, o-cresol novolac A epoxidized propyl ether type epoxy resin such as a varnish type epoxy resin or a polyphenol type epoxy resin is more preferable. Among them, bisphenol A type epoxy resin is particularly preferred.

The above-mentioned epoxy propyl ether type epoxy resin can be synthesized by condensing the corresponding phenols with epichlorohydrin in the presence of a strong base by a generally known method. The reaction can be carried out in a manner known per se in the art to which the present invention pertains.

In addition, commercially available products can also be used. For example, for the commercial products of bisphenol A type epoxy resin, jER 157S70, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (Mitsubishi Chemical Co., Ltd.) Company manufacturing) and so on. For the commercial product of the bisphenol F-type epoxy resin, Epikote 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Tohto Kasei Co., Ltd.), or the like can be used. For the commercial use of the phenol novolac type epoxy resin, Epikote 152, Epikote 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), DEN can be used. -438 (Dow Chemical Co., Ltd.) and the like. For the commercial products of o-cresol novolac type epoxy resin, EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Japan Chemicals Co., Ltd.) can be used. Manufacturing) and so on. As a commercial product of a polyhydric phenol type epoxy resin, Epikote 1032H60, Epikote YX-4000 (made by Mitsubishi Chemical Corporation), etc. can be used.

The epoxy equivalent of the epoxy resin (C) is preferably from 100 to 500 g/eq, more preferably from 150 to 400 g/eq. Among them, the epoxy equivalent is defined as the molecular weight of the epoxy resin equivalent to one epoxy group. ring The oxygen equivalent can be measured, for example, by a method defined by JIS K7236 (preferably, potentiometric titration).

The acid value of the epoxy resin (C) is preferably less than 30 mg-KOH/g, more preferably 10 mg-KOH/g or less.

Further, the weight average molecular weight of the epoxy resin (C) is preferably from 300 to 10,000, more preferably from 400 to 6,000, still more preferably from 500 to 4,800.

When the epoxy resin (C) is contained in the curable resin composition of the present invention, the content is preferably from 1 to 60 parts by mass based on 100 parts by mass of the total of the resin (A) and the resin (B). It is more preferably 50 parts by mass. When the content of the epoxy resin (C) is within the above range, the adhesion between the obtained cured film and the substrate tends to be excellent.

<Antioxidant (F)>

The antioxidant (F) may, for example, be a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or an amine-based antioxidant. Among them, a phenolic antioxidant is preferred in that the cured film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate. 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-p-tripentylphenyl, 3,9-di[2-{3 -(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[ 5,5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylenebis(6-t-butyl-3- Methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-t-butyl-4-methylphenol) 1,3,5- ginseng (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione, 3,3',3〃,5,5',5〃-hexa-t-butyl-a,a',a〃-( Mesitylene-2,4,6-triyl)tris-p-cresol, neopentyl quinone [propionic acid-3-(3,5-di-t-butyl-4-hydroxyphenyl)]ester, 2, 6-di-t-butyl-4-methylphenol, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10 -Tetra-t-butyldibenzo[d,f][1,3,2]dioxophosphane and the like.

Commercially available products can also be used as the phenolic antioxidant. Examples of commercially available phenolic antioxidants include Sumilizer (registered trademark) BHT, GM, GS, GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), and IRGANOX (registered trademark) 1010, 1076, 1330, and 3114. (The above are all manufactured by BASF Corporation).

Examples of the sulfur-based antioxidants include: 3,3'-dilaurate, 3,3'-thiodipropionate, and 3,3'-thiodipropionate. Ester, neopentyl pentoxide (3-lauryl thiopropionate), and the like. Commercially available products can also be used as the sulfur-based antioxidant. Examples of the sulfur-based antioxidants of the commercially available products include SUMILIZER (registered trademark) TPL-R and TP-D (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, decyl phenyl phosphite, and distearyl pentaerythritol diphosphoric acid. Ester, tetrakis(tridecyl)-1,1,3-cis (2-methyl-5-t-butyl-4-hydroxyphenyl)butane diphosphite, and the like. Commercially available products can also be used as the phosphorus-based antioxidant. Examples of commercially available phosphorus-based antioxidants include IRGAFOS (registered trademark) 168, 12, and 38 (all of which are BASF Corporation, ADK STAB 329K, ADK STAB PEP36 (all of which are manufactured by ADEKA).

Examples of the amine-based antioxidant include N, N'-di-second butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, and N,N'-dicyclohexyl. P-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, and the like. A commercial item can also be used for the said amine antioxidant. Examples of commercially available amine-based antioxidants include SUMILIZER (registered trademark) BPA, BPA-M1, and 4ML (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

When the curable resin composition of the present invention contains the antioxidant (F), the content thereof is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the total amount of the resin. The following is better. When the content of the antioxidant (F) is within the above range, the obtained cured film tends to have excellent heat resistance and pencil hardness.

<Interacting Agent (H)>

Examples of the surfactant (H) include a polysiloxane surfactant, a fluorine surfactant, and a fluorine atom-containing polyoxo surfactant.

As an example of the polyoxygenated surfactant, a surfactant containing a decane bond can be mentioned. Specific examples are: Toray Silicone DC3PA, the same series SH7PA, the same series DC11PA, the same series SH21PA, the same series SH28PA, the same series SH29PA, the same series SH30PA, polyether modified polyoxygenated oil SH8400 (trade name: Dow Made by Corning Toray 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 (manufactured by Momentive Performance Materials, Japan).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain.

Specifically, it can be mentioned as Fluorinert (registered trademark) FC430, the same series FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, The same series F183, the same series F489, the same series F554, the same series R30 (made by DIC Co., Ltd.); EFTOP (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352 (Mitsubishi Materials Electronics Co., Ltd. ); Surfllon (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (made by Asahi Glass Co., Ltd.); E5844 (made by Daikin Fine Chemicals Research Co., Ltd.).

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a decane bond or a fluorocarbon chain. Specifically, MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, the same series F443 (made by DIC Corporation), and the like can be given.

When the curable resin composition of the present invention contains the surfactant (H), the content thereof is 0.001% by mass or more and 0.2% by mass or less, based on the total amount of the curable resin composition of the present invention, and is 0.002% by mass. The above is preferably 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less. When the content of the surfactant (H) is within the above range, the flatness of the cured film can be made better.

<Polycarboxylic acid (G)>

The polyvalent carboxylic acid (G) is at least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids. The polyvalent carboxylic acid is a compound having two or more carboxyl groups; and the polycarboxylic acid anhydride is a dehydrated compound of a polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid (G) is preferably 3,000 or less, more preferably 1,000 or less.

Examples of the polycarboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-octyl-3- Alkenyl) succinic anhydride, 2-(2,4,6-trimethylindol-3-enyl) succinic anhydride, propylene tricarboxylic anhydride, 1,2,3,4-butane tetracarboxylic dianhydride, etc. Polycarboxylic acid anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3 -dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, cyclopentane An alicyclic polycarboxylic acid anhydride such as tetracarboxylic dianhydride; phthalic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, pyromellitic anhydride, trimellitic anhydride (trimellitic) Anhydride), benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, ethylene glycol bis(dehydrotrimellitic acid) ester, glycerol ginseng (to the water Pyromellitic acid ester, glycerol bis(dehydrotrimellitic acid) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dihydroxyl) -3-furanyl)naphthyl [1,2-c] an aromatic polycarboxylic acid anhydride such as furan-1,3-dione;

It can also be used: ADEKA HARDENER EH-700 (trade name (same as below), manufactured by ADEKA Co., Ltd.), RIKACID-HH, same series-TH, same series-MH, same series MH-700 (New Japan Physical and Chemical Co., Ltd.) Manufactured, etc., Epikinia 126, the same series YH-306, the same series DX-126 (manufactured by Oiled Shell Epoxy Co., Ltd.) and other commercial products.

Examples of the polyvalent carboxylic acid include chain-like polycarboxylic acids derived from oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and linear polycarboxylic anhydride. a polycyclic carboxylic acid; an alicyclic polycarboxylic acid such as a polycarboxylic acid derived from cyclohexane dicarboxylic acid or an alicyclic polycarboxylic acid anhydride; isophthalic acid, terephthalic acid, 1, 4, 5, 8- An aromatic polycarboxylic acid such as a polycarboxylic acid derived from naphthalenetetracarboxylic acid or an aromatic polycarboxylic acid anhydride;

Among them, the cured film is excellent in heat resistance, and in particular, it is difficult to reduce the transparency in the visible light region, and a chain carboxylic anhydride and an alicyclic polycarboxylic acid anhydride are preferable, and an alicyclic polycarboxylic acid anhydride is more preferable. .

When the curable resin composition of the present invention contains the polyvalent carboxylic acid (G), the content is preferably from 1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (A) and the resin (B), and from 2 to 20 parts by weight. The mass fraction is more preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G) is within the above range, the cured film is excellent in heat resistance and adhesion.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be: ester solvent (molecular-COO-, without -O- Solvent), ether solvent (-O-, solvent containing no COO-), ether ester solvent (solvent containing -COO- and -O-), ketone solvent (molecular-CO-) It is selected from the group consisting of a solvent containing no -COO-, an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, and dimethyl alum.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol 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, and diethyl ether. 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-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, an phenyl group Ethyl ether (phenetol), methyl anisole (methyl anisole) and the like.

The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene Alcohol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone, and the like.

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or mesitylene.

Examples of the guanamine 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 from 120 ° C to 180 ° C at 1 atm is preferred in terms of coatability and dryness. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether, 3-methoxybutyl acetate and 3-methoxy-1-butanol, and a mixture thereof A solvent is preferred.

The content of the solvent (E) is preferably from 60 to 95% by mass, more preferably from 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 from 5 to 40% by mass, more preferably from 5 to 30% by mass. When the content of the solvent (E) is within the above range, the film coated with the curable resin composition tends to have high flatness.

<Other ingredients>

The curable resin composition of the present invention may contain a filler, another polymer compound, a thermal radical generator, an ultraviolet absorber, a chain transfer agent, a adhesion promoter, a thermal acid generator, etc., as needed. Additives known in the art.

The filler may, for example, be glass, silica, alumina or the like.

Other polymer compounds include thermosetting resins such as maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. ) such as thermoplastic resin.

Specific examples of the thermal radical generating agent 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 and 2,4-diphenyl-4-methyl-1-pentene.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, and 3-epoxypropyl oxypropyl trimethoxy decane. , 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3- Chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxyoxane, 3-thiopropyltrimethoxy Decane, 3-isocyanatepropyltriethoxyoxane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3- Aminopropylmethyldiethoxyoxane, N-2-(aminoethyl)-3-aminopropyltrimethoxyoxane, N-2-(aminoethyl)-3-aminopropylmethyl Diethoxy oxane, 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy decane, N-phenyl-3-aminopropyltrimethoxy decane, N-phenyl-3-amine Propyl triethoxy oxane and the like.

Examples of the thermal acid generator include a thermal acid generator described in JP-A-2010-152335.

The curable resin composition of the present invention contains substantially no coloring agent such as a pigment or a dye. In other words, the content of the coloring agent in the curable resin composition of the present invention 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 heated quartz cell having an optical path length of 1 cm, and a spectrophotometer is used to measure the transmittance at a measurement wavelength of 400 to 700 nm. The transmittance is preferably 70% or more, and more preferably 80% or more.

When the curable resin composition of the present invention is used as a cured film, the average transmittance of the cured film is preferably 90% or more, more preferably 95% or more. The average transmittance is a spectrophotometer using a spectrophotometer for a cured film having a thickness of 2 μm after heat hardening (for example, 100 to 250 ° C for 5 minutes to 3 hours), and the average value at a measurement wavelength of 400 to 700 nm is measured. With this, A cured film excellent in transparency in the visible light range can be provided.

<Method for Producing Curable Resin Composition>

The curable resin composition of the present invention can be obtained by a resin (A) and a resin (B), and a solvent (E), an epoxy resin (C), and an antioxidant (which are used as required) by a generally known method. F), a surfactant (H), a polyvalent carboxylic acid (G), and other components are mixed and produced. After mixing, it is preferred to carry out filtration using a filter having a pore diameter of about 0.05 to 1.0 μm.

<Method for Producing Cured Film>

In the cured film formed of the curable resin composition of the present invention, the curable resin composition of the present invention can be applied onto a substrate and then thermally cured.

More specifically, the method for producing a cured film of the present invention comprises the following steps (1) to (3).

Step (1) Step of coating the curable resin composition of the present invention on a substrate

Step (2) Step of drying the coated curable resin composition under reduced pressure to form a composition layer

Step (3) Step of heating the composition layer

The step (1) is a step of applying the curable resin composition of the present invention to a substrate.

Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and/or a driving circuit may be formed on the substrate.

The coating on the substrate is preferably: a spin coater, a slit spin coater, a slit coater, an inkjet coater, a roll coater, a dip coater, etc. Set it up.

The step (2) is a step of drying the coated curable resin composition under reduced pressure to form a composition layer. By performing this step, volatile components such as a solvent in the curable resin composition can be removed.

Drying under reduced pressure is preferably carried out at a temperature of from 20 to 25 ° C at a pressure of from 50 to 150 Pa.

Heat drying (pre-bake) may also be carried out before or after drying under reduced pressure. Heating and drying are generally carried out using a heating device such as an oven or a heating plate. The temperature at which the drying is carried out is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Moreover, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

Step (3) is a step of heating the composition layer (post-baking). By heating, the composition layer can be hardened to form a cured film. Heating is generally carried out using a heating device such as an oven or a heating plate. The heating temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The heating time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

The cured film obtained in this manner is particularly excellent in flatness. Therefore, it can be used as a color filter substrate and a touch panel used in, for example, a liquid crystal display device, an organic EL display device, and an electronic book. Membrane and sheath. Thereby, a display device having a high-quality cured film can be manufactured. (Example)

Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are not particularly limited, that is, mass% and mass parts.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L/min to obtain a nitrogen gas atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and heated to 70 ° C while stirring. . Next, 40 parts by mass of methacrylic acid; and a mixture of the monomer (I-1) and the monomer (II-1) {monomer (I-1) in the mixture: the molar of the monomer (II-1) The ratio = 50:50} 360 parts was dissolved in 190 parts of diethylene glycol ethyl methyl ether to prepare a solution, and the solution was consumed in a dropping funnel for 4 hours, and dropped into a flask kept at 70 °C.

On the other hand, it took another 5 hours to pump in another drop, and 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in the flask. A solution of diethylene glycol ethyl methyl ether in 240 parts. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a 42.3% solid copolymer (resin Aa) solution. The obtained resin Aa had a weight average molecular weight of 8,000, a molecular weight distribution of 1.91, an acid value of 60 mg-KOH/g in terms of solid content, and an epoxy equivalent of 257 g/eq. The resin Aa has the following structural unit.

Synthesis Example 2

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and then 248 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C while stirring. Next, 63 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1), and a monomer (I-1) in the mixture: monomer (II-1) were added dropwise over 4 hours. Mole ratio = 50: 50} 27 parts, 105 parts of styrene, 105 parts of methyl methacrylate and 195 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 12 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 245 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 30.4% solid copolymer (resin Ba) solution. The obtained resin Ba had a weight average molecular weight of 2,1900, a molecular weight distribution of 2.11, an acid value of 152 mg-KOH/g in terms of solid content, and an epoxy equivalent of 2147 g/eq. The resin Ba has the following structural unit.

Synthesis Example 3

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and then 200 parts of diethylene glycol ethyl methyl ether was added, and heated to 85 ° C while stirring. Next, 63 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1), and a monomer (I-1) in the mixture: monomer (II-1) were added dropwise over 4 hours. Moerby = 50: 50} 42 parts, a mixed solution of 315 parts of styrene and 195 parts of diethylene glycol ethyl methyl ether. On the other hand, a mixed solution of 44 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 200 parts of diethylene glycol ethyl methyl ether was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 5 hours, and then cooled to room temperature to obtain a copolymer (resin Bb) solution having a solid content of 43.7%. The obtained resin Bb had a weight average molecular weight of 8,500, a molecular weight distribution of 1.90, an acid value of 95 mg-KOH/g in terms of solid content, and an epoxy equivalent of 2241 g/eq. The resin Bb has the following structural unit.

Synthesis Example 4

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and 245 parts of propylene glycol monomethyl ether acetate was further added thereto, and the mixture was heated to 85 ° C while stirring. Next, 73.5 parts of methacrylic acid, a mixture of the monomer (I-1) and the monomer (II-1), and a monomer (I-1) in the mixture: monomer (II-1) were added dropwise over 4 hours. A molar solution of molar ratio = 50:50} 31.5 parts, 122.5 parts of styrene, 122.5 parts of methyl methacrylate, and 160 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 35 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Bc) solution having a solid content of 38.0%. The obtained resin Bc The weight average molecular weight was 7,400, the molecular weight distribution was 1.75, the acid value of the solid fraction was 137 mg-KOH/g, and the epoxy equivalent was 2,096 g/eq. The resin Bc has the following structural unit.

Synthesis Example 5

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and then 256 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C while stirring. Next, 81 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1), and a monomer (I-1) in the mixture: monomer (II-1) were added dropwise over 4 hours. Mole ratio = 50: 50} 27 parts, 144 parts of styrene, 48 parts of methyl methacrylate, and 184 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 12 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 248 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 29.7% solid copolymer (resin Bd) solution. The obtained resin Bd had a weight average molecular weight of 21,000, a molecular weight distribution of 2.07, an acid value of 187 mg-KOH/g in terms of solid content, and an epoxy equivalent of 1984 g/eq. The resin Bd has the following structural unit.

Synthesis Example 6

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and 230 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C while stirring. Secondly, it took 4 hours to drip 60 parts of acrylic acid, a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molybdenum of monomer (II-1) A ratio of =50:50}24 parts, 91 parts of styrene, 91 parts of methyl methacrylate, 140 parts of propylene glycol monomethyl ether acetate, and 115 parts of 3-methoxy-1-butanol. On the other hand, a mixed solution of 11 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 238 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 26.7% solid copolymer (resin Be) solution. The obtained resin Be had a weight average molecular weight of 22,300, a molecular weight distribution of 2.19, an acid value of 201 mg-KOH/g in terms of solid content, and an epoxy equivalent of 2060 g/eq. The resin Be has the following structural unit.

Synthesis Example 7

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02 L/min to make a nitrogen gas atmosphere, and then 410 parts of diethylene glycol methyl ether was added, and heated to 85 while stirring. °C. Next, 259 parts of styrene, 34.5 parts of glycidyl methacrylate, and 51.7 parts of methacrylic acid were dissolved in 145 parts of diethylene glycol methyl ether to prepare a solution, and the dropping funnel took 3 hours. The solution was dropped into a flask maintained at 85 °C. On the other hand, 34.5 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in diethylene glycol methyl ether by using another dropping funnel for 3 hours. The solution in 60 parts was dropped into the flask. After completion of the dropwise addition of each solution, the mixture was kept at 85 ° C for 5 hours, and then cooled to room temperature to obtain a 33.8% solution of a copolymer (resin Bf) in a solid form. The obtained resin Bf had a weight average molecular weight of 9,100, a molecular weight distribution of 1.76, an acid value of 89 mg-KOH/g in terms of solid content, and an epoxy equivalent of 1,458 g/eq. The resin Bf has the following structural unit.

Synthesis Example 8

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02 L/min to form a nitrogen gas atmosphere, and then 230 parts of diethylene glycol ethyl methyl ether was added, and heated while stirring. To 80 ° C. Next, 60 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {monomer ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 340 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) 13 parts dissolved In 380 parts of diethylene glycol ethyl methyl ether, a solution was prepared, and the solution was dropped into the flask by a dropping liquid for 5 hours. After the completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 80 ° C for 3 hours, and then allowed to cool to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 42.5%. The obtained resin Ab had a weight average molecular weight of 14,000, a molecular weight distribution of 2.28, an acid value of 95 mg-KOH/g, and an epoxy equivalent of 291 g/eq. The resin Ab has the following structural unit.

<Measurement of molecular weight>

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin were measured by the GPC method under the following conditions.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

Standards for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The weight average molecular weight of the converted polystyrene obtained in the above And the ratio of the number average molecular weight (Mw / Mn) as a molecular weight distribution.

<Measurement of Epoxy Equivalent>

0.2 g of the resin solution obtained above was weighed in a 50 mL plug-in Erlenmeyer flask, and then 5 mL of toluene and 20 mL of acetic acid were added to prepare a sample for measurement. Further, one drop of a 1% crystal violet/acetic acid solution as an indicator was added to the sample for measurement, and titrated with a 0.1 N hydrogen bromide/acetic acid solution, and an epoxy equivalent was obtained according to the following formula [g/eq] ].

Epoxy equivalent = W × N × 100 / B × F

B: amount of 0.1 N hydrogen bromide/acetic acid solution consumed until the end of the titration (mL)

F: the factor of 0.1N hydrogen bromide / acetic acid solution (factor)

W: the amount of the measurement sample used for titration (g)

N: solid content (%) of the above obtained resin solution

Examples 1 to 9 and Comparative Example 1

<Preparation of Curable Resin Composition>

The components shown in Table 1 were mixed at a ratio shown in Table 1 to obtain a curable resin composition.

In addition, in Table 1, the content of the resin (A) and the resin (B) is a mass part of the converted solid content.

Resin (A): Aa, Ab

Resin (B): Ba to Bf

Epoxy resin (C): Ca: bisphenol A type epoxy resin (JER 157S70: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 210 g/eq)

Epoxy resin (C): Cb: monoallyl propylene oxide isopropyl isocyanuric acid (MA-DGIC: manufactured by Shikoku Chemical Co., Ltd., epoxy equivalent 140 g/eq)

Antioxidant (F): 1,3,5-gin (4-hydroxy-3,5-di-t-butylbenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione (IRGANOX (registered trademark) 3114: manufactured by BASF Corporation)

Polycarboxylic acid (G): butane tetracarboxylic acid (RIKACID BT-W: manufactured by New Japan Physical and Chemical Co., Ltd.)

Surfactant (H): Ha: Polyether modified polyoxyxide oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.)

Surfactant (H): Hb: MEGAFAC (registered trademark) E489 (manufactured by DIC Corporation)

Solvent (E): Ea: diethylene glycol ethyl methyl ether

Solvent (E): Eb: propylene glycol monomethyl ether acetate

Solvent (E): Ec: 3-methoxy-1-butanol

Solvent (E): Ed: 3-methoxybutyl acetate

Solvent (E): Ee: diethylene glycol monobutyl ether acetate

Further, the solvent (E) is a value of the solvent (Ea) to (Ee) in the solvent (E) as shown in Table 1, and the solid content of the curable resin composition is "solid" in Table 1. Mix in portions (%).

<Measurement of composition penetration rate>

The average transmittance (%) of 400 to 700 nm was measured for each curable resin composition by ultraviolet-visible near-infrared spectrophotometer (V-650: manufactured by JASCO Corporation) (quartz tube, optical path: 1 cm) . The results are shown in Table 3.

<Production of hardened film>

A 2 inch square glass substrate (EAGLE XG: manufactured by Corning) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and dried. The curable resin composition was spin-coated on the glass substrate so that the film thickness after post-bake was 2.0 μm, and then pre-baked at 90 ° C for 3 minutes in a dust-free oven. Thereafter, it was post-baked at 230 ° C for 40 minutes to obtain a cured film.

<Measurement of film thickness>

The film thickness of the cured film was measured by a contact type film thickness measuring device (DEKTAK6M: manufactured by ULVAC Co., Ltd.) at a measurement width of 500 μm and a measurement rate of 10 seconds.

<Measurement of the penetration rate of the cured film>

The transmittance (%) of the obtained cured film at 400 nm and the average transmittance (%) at 400 to 700 nm were measured using a microscopic spectrophotometer (OSP-SP200: manufactured by OLYMPUS). The results are shown in Table 3.

<Evaluation of Flatness: Production of Evaluation Substrate>

The components shown in Table 2 were mixed at the ratios shown in Table 2 to obtain Color photosensitive resin composition.

A 2 inch square glass substrate (EAGLE XG: manufactured by Corning) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and dried. The colored photosensitive resin composition was spin-coated on the glass substrate, and then prebaked in a dust-free oven at 90 ° C for 3 minutes to form a colored composition layer. After the cooling, the distance between the colored composition layer on the substrate and the quartz glass mask was 100 μm, and an exposure machine (TME-150RSK: TOPCON Co., Ltd., light source: ultrahigh pressure mercury lamp) was used for the large gas. In the environment, the light was irradiated with light having an exposure amount of 100 mJ/cm ² (base of 365 nm). Further, the light irradiation system passes light emitted from the ultrahigh pressure mercury lamp through an optical filter (UV-35: manufactured by Asahi Techno Glass Co., Ltd.). Further, in the case of the reticle, a reticle for forming a pattern of line and space having a line width of 30 μm was used. The colored composition layer after the illuminating was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 28 ° C for 80 seconds, and after washing with water, 220 in an oven. After the post-baking was carried out for 20 minutes at ° C, a substrate for evaluation of a colored pattern having a line width of 30 μm in line width was prepared. The film thickness of the coloring pattern formed on the evaluation substrate was measured and found to be 1.4 μm.

<Evaluation of flatness>

The evaluation substrate was applied by using a spin coater, and the film thickness after the subsequent baking was 1.5 μm. Thereafter, it was prebaked at 100 ° C for 3 minutes in a dust-free oven. After leaving to cool, a cured film was formed by post-baking at 230 ° C for 40 minutes.

The thickness of the portion of the cured film on the evaluation substrate that was in contact with the glass substrate to form a cured film was measured and determined to be 1.5 μm. The difference in the undulation of the surface of the cured film formed on the colored pattern was measured in the same manner as the film thickness measurement. When the height difference is 0.4 μm or less, the flatness of the cured film is good, and it is particularly useful as a protective film for a color filter. The results are shown in Table 3.

From the results of Table 3, it was confirmed that the cured film obtained by the curable resin composition of the present invention has good flatness.

(industrial availability)

According to the curable resin composition of the present invention, a cured film excellent in flatness can be produced.

Claims (5)

A curable resin composition comprising a resin (A) and a resin (B), and a content ratio of the resin (A) to the resin (B) is 40:60 to 90:10 by mass; a resin (A) a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. a structural unit having an epoxy equivalent of 200 g/eq or more and 500 g/eq or less; and the resin (B) containing a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and It is a structural unit of a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond, and has an epoxy equivalent of 1200 g/eq or more and 2600 g/eq or less. The curable resin composition according to claim 1, which further contains an antioxidant. The curable resin composition according to claim 1 or 2, which further contains a solvent. A cured film formed of the curable resin composition according to any one of claims 1 to 3. A display device comprising the cured film of claim 4 of the patent application.