KR20120022577A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to form a coating film having excellent drug resistance at the curing temperature under 200 °C. CONSTITUTION: A curable resin composition comprises: a copolymer containing a unit structure originated from at least one kind selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a unit structure originated from a monomer having carbon-carbon unsaturated double bond, and a structure epoxidized of unsaturated cycloaliphatic hydrocarbon, and having the acid value of 30-180 mg-KOH/g; an epoxy resin with the acid value of 30 mg-KOH/g or less; a compound having two of at least one kind of a group selected from acryloyl group and methacryl group, a thermal acid generator, and solvent.

Description

Curable Resin Composition {CURABLE RESIN COMPOSITION}

The present invention relates to a curable resin composition.

In a liquid crystal display, etc., in order to form overcoat, curable resin composition is used. As such a curable resin composition, curable resin composition containing the copolymer of methacrylic acid and 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate, dipentaerythritol hexaacrylate, and a solvent, for example. This is known. Moreover, it is known to apply | coat this curable resin composition to a board | substrate, bake at 220 degreeC for 20 minutes, and form a coating film (patent document 1).

On the other hand, in recent years, in order to realize a lighter and thinner liquid crystal display, development of a plastic liquid crystal display is anticipated. However, the heat resistance temperature of a typical plastic substrate is 100? It is only about 200 degreeC (nonpatent literature 1).

Moreover, when curable resin composition conventionally proposed is hardened at low temperature below 200 degreeC, and the coating film was formed, the chemical resistance of the formed coating film may not necessarily be enough.

Japanese Unexamined Patent Publication No. 2009-149854

 Sharp Kibo, No. 85, 30? 33 pages, April 2003

This invention is the following [1]? [6] to provide.

[1] The following (A), (B), (C), (D) and (E) are contained, and content of (B) is 1 mass part or more and 100 mass parts with respect to 100 mass parts of content of (A). Curable resin composition which is the following.

(A) It is derived from the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, the structure which epoxidized unsaturated alicyclic hydrocarbon, and the monomer which has a carbon-carbon unsaturated double bond. A copolymer containing the structural unit to make, and whose acid value is 30 mg-KOH / g or more and 180 mg-KOH / g or less

(B) an epoxy resin having an acid value of less than 30 mg-KOH / g

(C) The compound which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group.

(D) thermal acid generator

(E) solvent

[2] at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (I) in which a monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond Curable resin composition as described in said [1].

[Formula 1]

[In formula (I) and formula (II), R <^1> and R <^2> respectively independently represents a hydrogen atom or C1-C? The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² are each independently a single bond or 1? The alkanediyl group of 6 is represented and -CH ₂ -contained in the alkanediyl may be substituted with -O-, -S-, or -NR ^3- . R ³ represents a hydrogen atom or 1? 4 represents an alkyl group]

[3] Curable resin composition as described in said [1] or [2] whose molecular weight of the compound which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group is 150 or more and 3000 or less.

[4] above [1]? Coating film formed using curable resin composition in any one of [3].

[5] above [1]? Coating film formed by apply | coating curable resin composition in any one of [3] to a board | substrate, and hardening by heat.

[6] A display device comprising the coating film as described in the above [4] or [5].

Hereinafter, the present invention will be described in detail.

Curable resin composition of this invention contains following (A), (B), (C), (D) and (E), and content of (B) is 1 mass with respect to 100 mass parts of (A) content It is curable resin composition which is more than 100 parts by mass.

 (A) It is derived from the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, the structure which epoxidized unsaturated alicyclic hydrocarbon, and the monomer which has a carbon-carbon unsaturated double bond. A copolymer containing the structural unit to make, and whose acid value is 30 mg-KOH / g or more (Hereinafter, it may be called "resin (A).))

(B) Epoxy resin whose acid value is less than 30 mg-KOH / g (Hereinafter, it may be called "epoxy resin (B).))

(C) Compound which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group (Hereinafter, it may be called "polymerizable compound (C).")

(D) thermal acid generator

(E) solvent

In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

Curable resin composition of this invention contains resin (A). Resin (A) is a structural unit derived from at least 1 sort (a) (hereinafter may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and unsaturated alicyclic type It is a copolymer containing the structural unit derived from the monomer (b) (Hereinafter, it may be called "(b)") which has a structure which epoxidized hydrocarbon and a carbon-carbon unsaturated double bond, and is the acid of resin (A). It is thin 30 mg-KOH / g or more and 180 mg-KOH / g or less.

As resin (A) used for curable resin composition of this invention, for example,

Resin (A2-1): copolymer formed by superposing | polymerizing (a) and (b), and

Resin (A2-2): Monomer (c) copolymerizable with (a), (b), (a) and (b) (however, there is no structure epoxidized unsaturated alicyclic hydrocarbon) (hereinafter " (c) "may be mentioned. The copolymer etc. which superpose | polymerize, etc. are mentioned, As resin (A), resin (A2-1) is preferable.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3? Vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups, such as cyclo [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyl oxyalkyl of a bivalent or more polyvalent carboxylic acid, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization reactivity or alkali solubility.

Here, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (b), For example, vinylcyclohexene monooxide, a 1, 2- epoxy- 4-vinyl cyclohexane (for example, serotokiside 2000; Daicel Chemical Industry Co., Ltd. product), 3, 4- Epoxycyclohexylmethyl acrylate (for example, cycloma A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cycloma M100; diecel chemical industry ( Note) manufacture), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula 2]

[In formula (I) and formula (II), R <^1> and R <^2> respectively independently represents a hydrogen atom or C1-C? The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² are each independently a single bond or 1? The alkanediyl group of 6 is represented and -CH ₂ -contained in the alkanediyl may be substituted with -O-, -S-, or -NR ^3- . R ³ represents a hydrogen atom or 1? 4 represents an alkyl group]

Carbon number 1? As an alkyl group of 4, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. are mentioned specifically ,.

Examples of the hydroxyalkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned. Can be.

As R <^1> and R <^2> , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane- 1, 6- diyl group etc. are mentioned.

Roneun X ¹ and X ^2, and preferably include a single bond, methylene group, ethylene group, * -CH ₂ -O- (* indicates the number of engagement with the O) group, * -CH ₂ CH ₂ -O- group and there may be mentioned more preferably a single bond, * -CH may be mentioned ₂ CH ₂ -O- group, more preferably a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), it is a formula (I-1)? The compound etc. which are represented by Formula (I-15) are mentioned. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), and formula (I-11)? Formula (I-15) is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

(3)

As a compound represented by Formula (II), it is a formula (II-1)? The compound etc. which are represented by Formula (II-15) are mentioned. Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11)? Formula (II-15) is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

[Formula 4]

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. When mixing, the mixing ratio is a molar ratio, Preferably it is 5:95? 95: 5, More preferably, it is 10:90? 90:10, Especially preferably, it is 20:80? 80:20.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, etc. are mentioned, for example. (Meth) acrylic-acid alkylester of;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) (Meth) acrylic-acid cyclic alkylesters, such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto -2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di- (2′-hydroxyethyl) bicyclo [2.2.1] hepto -2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5- Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1 ] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Phenoxycarbonylbis Ro [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis (cyclohexyloxycarbonyl ) Bicyclo unsaturated compounds such as bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

As (c), in addition to the above, for example, a structure in which a chain olefin is epoxidized, a monomer having a carbon-carbon unsaturated double bond, a monomer having an oxetanyl group and a carbon-carbon unsaturated double bond, and a tetrahydropryl group and carbon The monomer etc. which have a carbon unsaturated double bond are mentioned.

As a monomer which has the structure which epoxidized the chain | strand-type olefin, and a carbon-carbon unsaturated double bond, specifically, glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, and (beta) -ethylglycol Cydyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glyc Cydyl 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 (glycidyloxymethyl) styrene, The compound described in Unexamined-Japanese-Patent No. 7-248625, etc. are mentioned.

As a monomer which has an oxetanyl group and a carbon-carbon unsaturated double bond, for example, 3-methyl-3- methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3 -Ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acrylic Royloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

Specific examples of the monomer having a tetrahydrofuryl group and a carbon-carbon unsaturated double bond include tetrahydrofurfuryl acrylate (for example, biscoat V ＃ 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofur. Furyl methacrylate etc. are mentioned.

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

In resin (A2-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit which comprises resin (A2-1).

structural unit derived from (a); 5? 60 mol% (more preferably 10-50 mol%)

structural unit derived from (b); 40? 95 mol% (more preferably 50-90 mol%)

When the ratio of the structural unit of the resin (A2-1) is in the above range, the storage stability, chemical resistance, heat resistance and mechanical strength tend to be good.

As resin (A2-1), resin (A2-1) which is a monomer which has a structure which epoxidized polycyclic unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is preferable, and (b) is a formula Resin (A2-1) which is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by (I) and a compound represented by Formula (II) is more preferable.

Resin (A2-1) is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki, Issuance Co., Ltd., First Edition, March 1, 1972). It can manufacture with reference to the cited document described in the literature.

Specifically, the method of stirring, heating, and keeping warm in deoxidation is illustrated by inject | pouring predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, Any of the thing normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide) Etc.) What is necessary is just to melt | dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of curable resin composition can be used.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, the solution after reaction can be used as it is by using the same solvent as the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, and a manufacturing process can be simplified.

In resin (A2-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total mole number of all the structural units which comprise resin (A2-2).

structural unit derived from (a); 2 ? 55 mol% (more preferably 5-45 mol%)

structural unit derived from (b); 2 ? 95 mol% (more preferably 5-80 mol%)

structural unit derived from (c); One ? 65 mol% (more preferably 1-60 mol%)

When the ratio of the structural unit of resin (A2-2) exists in the said range, storage stability, solvent resistance, heat resistance, and surface hardness tend to become favorable.

As resin (A2-2), resin (A2-2) which is a monomer which has a structure in which (b) epoxidized polycyclic unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is preferable, (b) is Resin (A2-2) which is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) is more preferable.

Resin (A2-2) can be manufactured by the method similar to resin (A2-1).

As a specific example of resin (A2-1), the copolymer of (meth) acrylic acid / formula (I-1), the copolymer of (meth) acrylic acid / formula (I-2), (meth) acrylic acid / formula (I -3) copolymer, copolymer of (meth) acrylic acid / formula (I-4), copolymer of (meth) acrylic acid / formula (I-5), air of (meth) acrylic acid / formula (I-6) Copolymer, copolymer of (meth) acrylic acid / formula (I-7), copolymer of (meth) acrylic acid / formula (I-8), copolymer of (meth) acrylic acid / formula (I-9), (meth) Copolymer of acrylic acid / formula (I-10), copolymer of (meth) acrylic acid / formula (I-11), copolymer of (meth) acrylic acid / formula (I-12), (meth) acrylic acid / formula (I -13) copolymer, (meth) acrylic acid / copolymer of formula (I-14), (meth) acrylic acid / copolymer of formula (I-15), (meth) acrylic acid / air of formula (II-1) Copolymer, copolymer of (meth) acrylic acid / formula (II-2), copolymer of (meth) acrylic acid / formula (II-3), copolymer of (meth) acrylic acid / formula (II-4), (meth) Acrylic acid / Copolymer of formula (II-5), (meth) acrylic acid / copolymer of formula (II-6), (meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / formula (II- 8) copolymer, copolymer of (meth) acrylic acid / formula (II-9), copolymer of (meth) acrylic acid / formula (II-10), copolymer of (meth) acrylic acid / formula (II-11) , Copolymer of (meth) acrylic acid / formula (II-12), copolymer of (meth) acrylic acid / formula (II-13), copolymer of (meth) acrylic acid / formula (II-14), (meth) acrylic acid / Copolymer of formula (II-15), (meth) acrylic acid / formula (I-1) / copolymer of formula (II-1), (meth) acrylic acid / formula (I-2) / formula (II-2 Copolymer of (meth) acrylic acid / formula (I-3) / formula (II-3), copolymer of (meth) acrylic acid / formula (I-4) / formula (II-4), (Meth) acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth) acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth) acrylic acid / formula ( I-7) / copolymer of formula (II-7), (meth) acrylic acid / formula ( I-8) / copolymer of formula (II-8), (meth) acrylic acid / copolymer of formula (I-9) / formula (II-9), (meth) acrylic acid / formula (I-10) / formula Copolymer of (II-10), copolymer of (meth) acrylic acid / formula (I-11) / formula (II-11), of (meth) acrylic acid / formula (I-12) / formula (II-12) Copolymer, copolymer of (meth) acrylic acid / formula (I-13) / formula (II-13), copolymer of (meth) acrylic acid / formula (I-14) / formula (II-14), (meth) Copolymer of acrylic acid / formula (I-15) / formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (I-7), (meth) acrylic acid / formula (I- 1) / copolymer of formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / air of formula (I-3) Copolymer, copolymer of crotonic acid / formula (I-4), copolymer of crotonic acid / formula (I-5), copolymer of crotonic acid / formula (I-6), crotonic acid / formula (I-7) Copolymer of crotonic acid / formula (I-8), copolymer of crotonic acid / formula (I-9), air of crotonic acid / formula (I-10) Sieve, copolymer of crotonic acid / formula (I-11), copolymer of crotonic acid / formula (I-12), copolymer of crotonic acid / formula (I-13), crotonic acid / formula (I-14) Copolymer of, crotonic acid / copolymer of formula (I-15), copolymer of crotonic acid / formula (II-1), copolymer of crotonic acid / formula (II-2), crotonic acid / formula (II- 3) copolymer, crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / formula ( Copolymer of II-7), copolymer of crotonic acid / formula (II-8), copolymer of crotonic acid / formula (II-9), copolymer of crotonic acid / formula (II-10), crotonic acid / Copolymer of formula (II-11), copolymer of crotonic acid / formula (II-12), copolymer of crotonic acid / formula (II-13), copolymer of crotonic acid / formula (II-14), croton Copolymer of acid / formula (II-15), copolymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2), copolymer of maleic acid / formula (I-3) , Maleic acid / formula (I-4) Copolymer of maleic acid / formula (I-5), copolymer of maleic acid / formula (I-6), copolymer of maleic acid / formula (I-7), maleic acid / formula (I-) 8) copolymer, maleic acid / copolymer of formula (I-9), maleic acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), maleic acid / formula ( I-12) copolymer, maleic acid / copolymer of formula (I-13), maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15), maleic acid / Copolymer of formula (II-1), copolymer of maleic acid / formula (II-2), copolymer of maleic acid / formula (II-3), copolymer of maleic acid / formula (II-4), male Copolymer of acid / formula (II-5), copolymer of maleic acid / formula (II-6), copolymer of maleic acid / formula (II-7), copolymer of maleic acid / formula (II-8) , Copolymer of maleic acid / formula (II-9), copolymer of maleic acid / formula (II-10), copolymer of maleic acid / formula (II-11), maleic acid / formula (II-12) Copolymer, maleic acid / copolymer of formula (II-13), maleic acid / air of formula (II-14) Copolymer, maleic acid / copolymer of formula (II-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1), (meth) acrylic acid / maleic anhydride / formula (I-2) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-5), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-6), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-7), (meth A copolymer of acrylic acid / maleic anhydride / formula (I-8), a copolymer of (meth) acrylic acid / maleic anhydride / formula (I-9), (meth) acrylic acid / maleic anhydride / formula (I-10) Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-11), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-12), (meth) acrylic acid / maleic acid Anhydride / copolymer of formula (I-13), (meth) acrylic acid / maleic anhydride / formula (I-14 Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1), (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (II-2), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-3), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-4), Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-5), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-6), (meth) acrylic acid / maleic anhydride / formula (II -7) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-8), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-9), (meth) acrylic acid / Copolymer of maleic anhydride / formula (II-10), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-11), air of (meth) acrylic acid / maleic anhydride / formula (II-12) Copolymer, (meth) acrylic acid / maleic anhydride / formula (II-13) And the like copolymer, (meth) acrylic acid / maleic anhydride / formula (Ⅱ-14) of the copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (Ⅱ-15).

As a specific example of resin (A2-2), the copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth) Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (I-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (I-7) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-9) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate Copolymer of (meth) acrylic acid / copolymer of formula (I-12) / methyl (meth) acrylate, ( Copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, (meth) acrylic acid / formula ( I-15) / Copolymer of methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-2) / methyl Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-3) / methyl (meth) acrylate, of (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (II-7) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate, (meth) acrylic acid / formula (II- 9) / Copolymer of methyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (II-10) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-11) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-12 Copolymer of () / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-14) / methyl (meth) Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, air of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclopentanyl (meth Copolymer of acrylate, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / dicyclopentanyl (meth) acrylate , (Meth) acrylic acid / maleic anhydride / formula (I-1) / di Copolymer of cyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, crotonic acid / formula (II-1) ) / Copolymer of dicyclopentanyl (meth) acrylate, maleic acid / formula (II-1) / copolymer of dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (II-1 ) / Copolymer of dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (I-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) Copolymer of / formula (II-1) / phenyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / phenyl (meth) acrylate, maleic acid / formula (I-1) / phenyl ( Aerial of meth) acrylate Sieve, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth ) Copolymer of acrylate, copolymer of crotonic acid / formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, (meth) Copolymer of acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylate, air of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / diethyl maleate, copolymer of (meth) acrylic acid / formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) ) / Copolymer of formula (II-1) / diethyl maleate, copolymer of crotonic acid / formula (I-1) / diethyl maleate, copolymer of maleic acid / formula (I-1) / diethyl maleate, Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / diethyl maleate, (meth) Copolymer of methacrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate, copolymer of crotonic acid / formula (II-1) / diethyl maleate, maleic acid / formula (II-1) / Copolymer of diethyl maleate, (meth) acrylic acid / maleic anhydride / formula (II-1) / copolymer of diethyl maleate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / Copolymer of diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (I-1) Copolymer of (2) -hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula Copolymer of (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate Copolymer of, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (II-1) / 2-hydroxyethyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I- 1) / Copolymer of bicyclo [2.2.1] hepto-2-ene, (meth) acrylic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hepto-2-ene, (meth) Copolymer of acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hepto-2-ene, crotonic acid / formula (I-1) / bicyclo [2.2.1] hepto Copolymer of 2-ene, maleic acid / formula (I-1) / bicyclo [2.2.1] hepto-2-ene copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / Vehicle Copolymer of rho [2.2.1] hepto-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hepto-2-ene, Copolymer of crotonic acid / formula (II-1) / bicyclo [2.2.1] hepto-2-ene, air of maleic acid / formula (II-1) / bicyclo [2.2.1] hepto-2-ene Copolymer, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / bicyclo [2.2.1] hepto-2-ene, (meth) acrylic acid / formula (II-1) / methyl (meth) Copolymer of acrylate / bicyclo [2.2.1] hepto-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II- 1) copolymer of / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, crotonic acid / formula (I-1) ) / N-cyclohexylmaleimide copolymer, maleic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / N- Copolymerization of Cyclohexyl Maleimide Copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide, Copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth) acrylic acid Copolymer of / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / styrene, (meth) acrylic acid / formula (II) -1) / copolymer of styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymer of crotonic acid / formula (I-1) / styrene, maleic acid Copolymer of / formula (I-1) / styrene, (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) Copolymer of acrylate / styrene, copolymer of crotonic acid / formula (II-1) / styrene, maleic acid / formula (II-1) / styrene Copolymer of styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / styrene, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / styrene, Copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, (meth A copolymer of acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene and a copolymer of crotonic acid / formula (I-1) / N-cyclohexylmaleimide / styrene , Copolymer of maleic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexylmaleimide / styrene , Copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene, crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene Copolymer of maleic acid / formula (II-1) / N-cyclohexylmale Copolymer of imide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / methyl ( And copolymers of meth) acrylate / N-cyclohexylmaleimide / styrene.

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000? 100,000, more preferably 5,000? 50,000, more preferably 6,000? 15,000. When the weight average molecular weight of resin (A) exists in the said range, applicability | paintability tends to become favorable, film | membrane decrease does not produce at the time of image development, and there exists a tendency for the omission of a non-pixel part at the time of image development to be favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. 6.0, more preferably 1.2? 4.0, more preferably 1.5? 3.0, particularly preferably 1.8? 2.8. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of resin (A) is 30 mg-KOH / g or more and 180 mg-KOH / g or less, Preferably it is 40 mg-KOH / g or more and 150 mg-KOH / g or less, More preferably, 50 mg-KOH / g or more and 135 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A), and can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is in the above range, it tends to be excellent in chemical resistance.

The content of the resin (A) is preferably 40? With respect to the total amount of the resin (A) and the polymerizable compound (C). 90 mass%, More preferably, it is 40? 80 mass%, Especially preferably, it is 40? 70 mass%. When content of resin (A) exists in the said range, there exists a tendency for chemical-resistance to become favorable.

Curable resin composition of this invention contains the epoxy resin (B) whose acid value is less than 30 mg-KOH / g. The acid value of an epoxy resin (B) becomes like this. Preferably it is 20 mg-KOH / g or less, More preferably, it is 10 mg-KOH / g or less. Here, an epoxy resin means the compound which has two or more oxylanyl groups, or a mixture thereof, and is not limited to a high molecular compound. It is preferable that the oxylanyl group which an epoxy resin (B) has is a structure which epoxidized chain olefin.

As an epoxy resin (B), a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. are mentioned, for example. These may use a commercial item. Commercially available bisphenol A type epoxy resins include Epicoat 828, Copper 1001, Copper 1002, Copper 1003, Copper 1004, Copper 1007, Copper 1009, Copper 1010 (above, manufactured by Mitsubishi Chemical Corporation), and the like. . As a bisphenol F-type epoxy resin marketed, Epicoat 807, 834 (above, Mitsubishi Chemical Corporation make), etc. are mentioned. As a phenol novolak-type epoxy resin marketed, Epicoat 152, Copper 154, Copper 157H65 (above, Mitsubishi Chemical Corporation make), EPPN201, Copper 202 (above, Nippon Kayaku Co., Ltd. make) etc. are mentioned. Can be. As a commercial cresol novolak-type epoxy resin, Sumiepoxy ESCN-195XL-80 (Sumitomo Chemical Co., Ltd. product), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN- 1027 (above, Nippon Kayaku Co., Ltd. make), Epicoat 180S75 (made by Mitsubishi Chemical Corporation), etc. are mentioned.

Moreover, as commercially available epoxy resins other than the above, CY175, CY177, CY179 (above, Asahi Kasei Material Co., Ltd. product), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above) , UCC Co., Ltd., Shodyne 509 (Showa Denko Co., Ltd.), Araldito CY-182, CY-192, CY-184 (above, manufactured by Asahi Kasei Chemicals), Epicro 200 Cyclic aliphatic epoxy resins such as Copper 400 (above, manufactured by DIC Corporation), Epicoat 871, Copper 872, EP1032H60 (above, manufactured by Mitsubishi Chemical Corporation); Aliphatic polyglycidyl ethers such as Epicoat 190P, copper 191P (above, manufactured by Mitsubishi Chemical Co., Ltd.), epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), and Epior TMP (manufactured by Nippon Oils & Fats Co., Ltd.) Can be mentioned.

Especially, as an epoxy resin (B), a bisphenol-A epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin are preferable.

Content of an epoxy resin (B) is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of content of resin (A), 5 mass parts or more and 70 mass parts or less are preferable, 5 mass parts or more and 50 mass parts The following is more preferable, 5 mass parts or more and 25 mass parts or less are more preferable, 5 mass parts or more and 10 mass parts or less are especially preferable.

When content of an epoxy resin (B) exists in the said range, there exists a tendency which is excellent in the flatness of the coating film obtained.

Curable resin composition of this invention contains the polymeric compound (C) which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group. It is preferable that they are 150 or more and 3000 or less, and, as for the molecular weight of a polymeric compound (C), it is more preferable that they are 200 or more and 1500 or less. When containing 2 or more polymeric compound (C), it is preferable that the weight average molecular weight of this mixture is the said range.

As a compound which has two at least 1 sort (s) of group chosen from the group which consists of acryloyl group and a methacryloyl group, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

As a compound which has 3 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and a methacryloyl group, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta (meth Reactant of an acrylate and an acid anhydride, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth ) Acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, propylene oxide modified dipentaerythritol penta (meth) acrylate, propylene oxide modified dipenta Erythritol hexa (meth) acrylate etc. are mentioned.

Especially, as a polymeric compound (C), the compound which has 3 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group is preferable, and trimethylol propane tri (meth) acrylate and dipenta Erythritol hexa (meth) acrylate is more preferable. If a polymeric compound (C) is these compounds, the coating film obtained will tend to be excellent in chemical resistance.

You may use together the compound which has at least 1 type of group chosen from the group which consists of acryloyl group and methacryloyl group to the extent which does not impair the effect of this invention.

As such a compound, (a), (b), (c) which are monomers which comprise resin (A), nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-ethyl Hexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. are mentioned.

The content of the polymerizable compound (C) is preferably 10? To the total amount of the resin (A) and the polymerizable compound (C). 60 mass%, More preferably, it is 20? 60 mass%, Especially preferably, it is 30? 60 mass%. When content of a polymeric compound (C) is in the said range, it exists in the tendency which was excellent in the intensity | strength, smoothness, and reliability of a coating film.

Curable resin composition of this invention contains a thermal acid generator (D). Thermal acid generators are compounds that generate acids by the action of heat. It is preferable that it is a compound which generate | occur | produces an acid below the temperature of the postbaking mentioned later.

Examples of the thermal acid generator (D) include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Examples of the sulfonium salts include (4-hydroxyphenyl) dimethylsulfonium bis (trifluoromethanesulfonyl) imide, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium bis (trifluoromethane Sulfonyl) imide, (4-hydroxyphenyl) benzylmethylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfoniumbis (trifluoro Methanesulfonyl) imide, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfonium bis (trifluoromethanesulfonyl) imide, (4-methoxycarbonyloxyphenyl) dimethylsulfonium bis (Trifluoromethanesulfonyl) imide, (4-methoxycarbonyloxyphenyl) benzylmethylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-methoxycarbonyloxyphenyl) (2- Methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-methoxycarbonyloxyphenyl) (4-methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) De, (4-acetoxyphenyl) benzylmethylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) (4-methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) Imide, (4-acetoxyphenyl) (2-methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) dimethylsulfonium bis (trifluoromethanesulfonyl) Imide and (4-acetoxyphenyl) (1-naphthylmethyl) methylsulfonium bis (trifluoromethanesulfonyl) imide;

(4-hydroxyphenyl) dimethylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium hexafluorophosphate, (4-hydroxyphenyl) benzylmethylsulfonium hexafluoro Phosphate, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfonium hexafluorophosphate, (4-acetoxy Phenyl) dimethylsulfonium hexafluorophosphate, (4-acetoxyphenyl) benzylmethylsulfonium hexafluorophosphate, (4-acetoxyphenyl) (2-methylbenzyl) methylsulfonium hexafluorophosphate, (4- Acetoxyphenyl) (4-methylbenzyl) methylsulfonium hexafluorophosphate, (4-acetoxyphenyl) (1-naphthylmethyl) methylsulfonium hexafluorophosphate;

(4-hydroxyphenyl) dimethylsulfonium trifluoromethanesulfonite, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-hydroxyphenyl) benzylmethylsul Phosphorium trifluoromethanesulfonite, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfoniumtrifluor Romethanesulfonite, (4-acetoxyphenyl) dimethylsulfoniumtrifluoromethanesulfonite, (4-acetoxyphenyl) benzylmethylsulfoniumtrifluoromethanesulfonite, (4-acetoxyphenyl) (2- Methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-acetoxyphenyl) (4-methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-acetoxyphenyl) (1-naphthylmethyl) Methylsulfonium trifluoromethanesulfonite;

(4-acetophenyl) dimethylsulfonium hexafluoroantimonate, (4-benzyloxycarbonyloxyphenyl) dimethylsulfonium hexafluoroantimonate, (4-benzoyloxyphenyl) dimethylsulfonium hexafluoroantimony Monate, (3-chloro-4-acetoxyphenyl) dimethylsulfonium hexafluoroantimonate, (4-hydroxyphenyl) benzylmethylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) benzyl Methylsulfonium hexafluoroantimonate, (4-methoxyphenyl) benzylmethylsulfonium hexafluoroantimonate, (4-hydroxy-2-methylphenyl) benzylmethylsulfonium hexafluoroantimonate, ( 4-hydroxyphenyl) bisbenzylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) bisbenzylsulfonium hexafluoroantimonate, (4-methoxyphenyl) bisbenzylsulfonium hexafluoroantimony Monate, (4-hydroxy-3-tert-butyl-5-methylphenyl) bisbenzylsulfonium hexaple Oroantimonate, (4-hydroxyphenyl) (4-chlorobenzyl) methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl) (4-nitrobenzyl) methylsulfonium hexafluoroantimonate , (4-hydroxy-3-methylphenyl) (4-nitrobenzyl) methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl) (3,5-dichlorobenzyl) methylsulfonium hexafluoroantimo Acetate, (4-hydroxy-3-chlorophenyl) (2-chlorobenzyl) methylsulfonium hexafluoroantimonate;

(4-acetoxyphenyl) dimethylsulfonium hexafluoroarsenate, (4-benzoyloxyphenyl) dimethylsulfonium hexafluoroarsenate, (3-chloro-4-hydroxyphenyl) benzylmethylsulfonium hexa Fluoroarsenate, (3-chloro-4-hydroxyphenyl) bisbenzylsulfonium hexafluoroarsenate;

(4-hydroxyphenyl) benzylmethylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (4-methoxybenzyl) methylsulfonium hexafluorophosphate, (4-hydroxyphenyl) bisbenzylsulfonium hexa Fluorophosphate, (4-hydroxyphenyl) (4-methoxybenzyl) benzylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (4-chlorobenzyl) methylsulfonium hexafluorophosphate, and the like. have.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3- (4-methoxybenzyl) benzothiazonium hexafluoroantimonate, and 2-methylsulfanyl-3-benzylbenzo. Thiazonium hexafluoroantimonate, 5-chloro-3-benzylbenzothiazonium hexafluoroantimonate; 3-benzylbenzothiazonium hexafluorophosphate; 3-benzyl benzothiazonium tetrafluoroborate etc. are mentioned.

Especially, as a thermal acid generator (D), a sulfonium salt and a benzothiazolium salt are preferable, a sulfonium salt is more preferable, and (4-hydroxyphenyl) benzyl methylsulfonium bis (trifluoromethanesulfonyl) is already De, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfoniumbis (trifluoro Romethanesulfonyl) imide, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfonium bis (trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) dimethylsulfonium bis (tri Fluoromethanesulfonyl) imide, (4-hydroxyphenyl) benzylmethylsulfonium bis (trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) (2-methylbenzyl) methylsulfonium bis ( Trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) (4-methylbenzyl) methylsulfoniumbis (trifluoromethanesulfonyl) imide, (4-acetoxyphenyl) (1- Peutil) methyl sulfonium bis-methanesulfonyl (trifluoromethyl) imide;

(4-hydroxyphenyl) benzylmethylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (4-methylbenzyl) Methylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfonium hexafluorophosphate, (4-acetoxyphenyl) dimethylsulfoniumtrifluoromethanesulfonite, (4- Acetoxyphenyl) benzylmethylsulfonium hexafluorophosphate, (4-acetoxyphenyl) (2-methylbenzyl) methylsulfonium hexafluorophosphate, (4-acetoxyphenyl) (4-methylbenzyl) methylsulfonium Hexafluorophosphate, (4-acetoxyphenyl) (1-naphthylmethyl) methylsulfonium hexafluorophosphate;

(4-hydroxyphenyl) dimethylsulfoniumtrifluoromethanesulfonite, (4-hydroxyphenyl) benzylmethylsulfoniumtrifluoromethanesulfonite, (4-hydroxyphenyl) (2-methylbenzyl) methylsul Phosphorium trifluoromethanesulfonite, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfoniumtrifluor Romethanesulfonite, (4-acetoxyphenyl) benzylmethylsulfoniumtrifluoromethanesulfonite, (4-acetoxyphenyl) (2-methylbenzyl) methylsulfoniumtrifluoromethanesulfonite, (4-acetyl Methoxyphenyl) (4-methylbenzyl) methylsulfonium trifluoromethanesulfonite, (4-acetoxyphenyl) (1-naphthylmethyl) methylsulfonium trifluoromethanesulfonite;

(4-hydroxyphenyl) benzylmethylsulfonium hexafluoroantimonate, (4-hydroxyphenyl) bisbenzylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) benzylmethylsulfonium hexafluoro At least one member selected from the group consisting of antimonate and (4-acetoxyphenyl) bisbenzylsulfonium hexafluoroantimonate is more preferable.

Examples of the thermal acid generator (D) include commercially available products such as Sanade SI-250, SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). You can also use

0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of total amounts of resin (A) and a polymeric compound (C), and, as for content of a thermal acid generator (D), 0.1 mass part or more and 5 mass parts or less are more preferable. desirable. When content of a thermal acid generator (D) is the said range, there exists a tendency for the visible light transmittance of a coating film to be high.

Curable resin composition of this invention contains a solvent (E).

The solvent (E) is not particularly limited as long as it can dissolve each component contained in the curable resin composition of the present invention. For example, ester solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-), ester It can select from ketone solvents (solvent containing -CO-) other than a solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc., and to use.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate and ethyl butyrate Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- pentanone, Cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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 solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl pyrrolidone.

These solvents may be used independently or may be used in combination of 2 or more type.

Among the above solvents, organic solvents having a boiling point of 100 ° C. or higher and 200 ° C. or lower at 1 atm are preferable in terms of coating properties and drying properties, and are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, and 3 More preferably, a solvent containing at least one selected from the group consisting of ethyl ethoxypropionate, 3-methoxybutyl acetate and 3-methoxy-1-butanol, and composed only of at least one selected from the group Solvent is more preferable.

Content of the solvent (E) in curable resin composition of this invention is 30? With respect to the total amount of curable resin composition. 95 mass% is preferable and 50? 90 mass% is more preferable, and 55? 85 mass% is more preferable. In other words, solid content of curable resin composition is 5? 70 mass% is preferable and 10? 50 mass% is more preferable, and 45 mass% is more preferable. Here, solid content means the quantity remove | excluding the solvent (E) from curable resin composition. When content of solvent (E) exists in the said range, application | coating when apply | coating with coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater and a curtain flow coater), an inkjet, a roll coater, etc. Excellent in sex

The curable resin composition of this invention may contain additives, such as a filler, another high molecular compound, an adhesion promoter, a thermal radical generating agent, a ultraviolet absorber, a chain transfer agent, as needed.

Glass, silica, alumina, etc. are mentioned as a filler.

As other high molecular compounds, thermosetting resins, such as a maleimide resin, thermoplastic resins, such as polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, and polyurethane, etc. are mentioned.

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- as adhesion promoters Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltri Methoxysilane, etc. are mentioned.

Specific examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Moreover, sodium polyacrylate etc. are mentioned specifically as a flocculant.

Examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

It is preferable that curable resin composition of this invention contains surfactant (F). As surfactant, a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (brand name: Toray Dow Corning Co., Ltd. product), 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 Co., Ltd.) Etc. can be mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain is mentioned. Specifically, Florinato (registered trademark) FC430, East FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaPac (registered trademark) F142D, East F171, East F172, East F173, East F177, East F183, East R30 (DIC) Co., Ltd.), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronics Chemicals Co., Ltd.), saffron (trademark) S381, copper S382, copper SC101, copper SC105 (Made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemicals Research Institute), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Park (registered trademark) R08, East BL20, East F475, East F477, East F443 (manufactured by DIC Corporation), and the like can be given. Preferably, Megapak (trademark) F475 is mentioned.

Content of surfactant (F) is 0.001 mass% or more and 0.2 mass% or less with respect to curable resin composition, Preferably they are 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. . By containing surfactant in the said range, flatness of a coating film can be made favorable.

Curable resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. That is, in the curable resin composition of this invention, content of the coloring agent with respect to the whole composition becomes like this. Preferably it is less than 1 mass%, More preferably, it is less than 0.5 mass%.

The curable resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and is measured wavelength 400? The average transmittance when the transmittance is measured under the conditions of 700 nm is preferably 70% or more, and more preferably 80% or more.

When making curable resin composition of this invention into a coating film, the average transmittance of a coating film becomes like this. Preferably it is 90% or more, and it is more preferable to become 95% or more. This average transmittance | permeability uses the spectrophotometer with respect to the coating film whose thickness after heat-hardening (for example, 120-240 degreeC, 10 minutes-120 minutes) is 2 micrometers, The measurement wavelength 400? It is the average value when it measures on conditions of 700 nm. Thereby, the coating film excellent in transparency in visible region can be provided.

The coating film of this invention can be produced by apply | coating curable resin composition of this invention on a board | substrate, and hardening by heat.

Glass, metal, plastics, etc. are mentioned as a board | substrate, A color filter, various insulating films or an electrically conductive film, a drive circuit, etc. may be formed on the board | substrate. Since the curable resin composition of this invention can be hardened at the temperature of 200 degrees C or less, a coating film can also be formed on the board | substrate with relatively low heat resistance like plastics.

In order to apply | coat the curable resin composition of this invention on a board | substrate, it can implement by using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

It is preferable to perform vacuum drying or prebaking after application | coating and to remove volatile components, such as a solvent.

The coating film from which the volatile component was removed 120? At 240 ° C., 10? The coating film can be formed by performing a 120 minute post-baking.

The film thickness of the coating film formed with curable resin composition of this invention is not specifically limited, What is necessary is just to adjust suitably by the material to be used, a use, etc .. For example, 0.1? 10 μm.

According to this invention, even if hardening temperature is less than 200 degreeC, the coating film excellent in chemical-resistance can be formed.

The coating film obtained in this way is useful as an overcoat used for a liquid crystal display device or an electronic paper, for example. Moreover, it can also be used for display apparatuses, such as a touch panel. Thereby, the display apparatus provided with the high quality coating film can be manufactured with high yield.

Example

Hereinafter, an Example demonstrates this invention in more detail. "%" And "part" in an example are the mass% and a mass part, unless there is particular notice.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. Then 40 parts of methacrylic acid; And molar ratio of monomer (I-1): monomer (II-1) in the mixture @ mixture of monomer (I-1) and monomer (II-1) = 50: 50｝ 360 parts, Diethylene glycol ethyl methyl ether 190 parts The solution dissolved in was prepared, and this solution was dripped in the flask heated to 70 degreeC over 4 hours using the dropping pump.

[Chemical Formula 5]

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was dripped at the flask over 5 hours using another dropping pump. It was. After completion of the dropwise addition of the polymerization initiator solution, the mixture was held at 70 ° C for 4 hours, then cooled to room temperature, to obtain a solution of a copolymer (resin Aa) having a solid content of 42.3%. As for the weight average molecular weight (Mw) of obtained resin Aa, 8000 and molecular weight distribution (Mw / Mn) were 1.91, and the acid value was 60 mg-KOH / g.

Synthesis Example 2

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. Heated to 70 ° C. Subsequently, 60 parts methacrylic acid; And molar ratio of monomer (I-1) to monomer (II-1) in the mixture ｛mixture of monomer (I-1) and monomer (II-1) = 50:50 Pa 240 parts, 140 parts of 3-methoxybutyl acetate The solution dissolved in was prepared, and this solution was dripped in the flask heated to 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was dripped at the flask over 4 hours using another dropping funnel. It was. After dripping of the polymerization initiator solution was complete | finished, it hold | maintained at 70 degreeC for 4 hours, it cooled to room temperature after that, and obtained the solution of the copolymer (resin Ab) of 32.6% of solid content. The weight average molecular weight (Mw) of obtained resin Ab was 13,400, molecular weight distribution (Mw / Mn) was 2.50, and the acid value was 113.9 mg-KOH / g.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of obtained resin Aa and resin Ab was performed on condition of the following using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

EXAMPLE 1

To 142 parts (60 parts in terms of solid content) of the solution of Resin Aa obtained in Synthesis Example 1,

Polymerizable compound (C): trimethylolpropane triacrylate (A-TMPT; Shinnakamura Chemical Co., Ltd. make, molecular weight: 296) 40 parts,

Resin (B): 10 parts of orthocresol novolak-type epoxy resins (Sumiepoxy ESCN-195XL-80; Sumitomo Chemical Co., Ltd. product, acid value: 0.1 mg-KOH / g),

Thermal acid generator (D): (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium bis (trifluoromethanesulfonyl) imide (SI-250; manufactured by Sanshin Chemical Co., Ltd.)

1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ( 1.0 part of IRGANOX 3114 (made by Chiba Japan Co., Ltd.) and a solvent (E) were mixed and the curable resin composition 1 was obtained. The solvent is mixed so that the mass ratio of propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and diethylene glycol ethyl methyl ether is 20:20:60, and the solid content of the curable resin composition 1 is 17.7%. It was.

EXAMPLE 2

Trimethylolpropane triacrylate was replaced with dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., molecular weight: 578), and 1,3,5-tris (4-hydroxy-3,5 Curable resin composition in the same manner as in Example 1 except that di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione was not used. 2 was obtained.

EXAMPLE 3

Curable resin composition 3 was obtained like Example 1 except having replaced trimethylol propane triacrylate with dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd. product).

[Comparative Example 1]

Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 1,3,5-tris to 184 parts (60 parts in terms of solid content) of the resin solution containing the resin Ab obtained in Synthesis Example 2 ( 3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (IRGANOX 3114; manufactured by Chiba Japan Co., Ltd.) 0.8 part and solvent were mixed and the curable resin composition 4 was obtained. The solvent has a mass ratio of propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy-1-butanol, and 3-methoxybutyl acetate to be 14: 20: 33: 33, and curable resin It mixed so that solid content of the composition 4 might be 17.7%.

<Average transmittance of the composition>

About the obtained curable resin composition, it was 400? Using an ultraviolet visible near-infrared spectrophotometer (V-650; Nippon Spectroscopy Co., Ltd. product) (quartz cell, optical path length; 1 cm), respectively. The average transmittance (%) at 700 nm was measured. The results are shown in Table 1.

<Production of coating film>

A 2 inch square glass substrate (Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water and 2-propanol, and dried. After spin-coating curable resin composition on this glass substrate and prebaking at 100 degreeC for 3 minutes, it post-baked at 150 degreeC for 60 minutes. After cooling, the film thickness of this coating film was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the thickness was 2.0 µm.

<Transmittance measurement>

The obtained coating film was the transmittance | permeability (%) and 400 to 400 nm using a microscopic spectrophotometer (OSP-SP200; OLYMPUS company make). The average transmittance (%) at 700 nm was measured. The results are shown in Table 1.

<Chemical resistance>

The obtained coating film was immersed in 30 degreeC N-methylpyrrolidone for 30 minutes, the film thickness before and after immersion was measured, and the film thickness change (%) and the transmittance change (%) were calculated | required according to following Formula. . In all, the closer to 100%, the smaller the change before and after immersion. When the film thickness change (%) is close to 100%, it is preferable because there is little dissolution or swelling of the film. When the transmittance change (%) is close to 100%, it is preferable because there is little coloring or discoloration of the coating film.

Film thickness change (%); (Film thickness after immersion (μm) / film thickness before immersion (μm)) × 100

Transmittance change (%); (Transmittance after immersion (%) / transmittance before immersion (%)) × 100

Moreover, the adhesive test was done with respect to the coating film after immersion. The coating film after immersion was cut out at intervals of 1 mm by using a cutter and a super cutter guide (manufactured by Thai Oil Substrate Co., Ltd.) to prepare 100 meshes of 1 mm × 1 mm. Subsequently, a tape (registered trademark) 24 mm width (manufactured by Nichiban Co., Ltd.) was applied to the mesh cut out of the coating film, and the tape was applied to the coating film by rubbing with an eraser on the tape with a cell. The tape was peeled off at once while holding the end of the tape and maintaining the right angle to the coating film surface. Thereafter, the number of meshes remaining on the substrate was visually counted without peeling the coating film. The larger the number of meshes remaining on the substrate, the better the adhesion.

Example 1 Example 2 Example 3 Comparative Example 1 Permeability (%) of curable resin composition 98.8 98.8 98.8 99.2 Transmittance of Coating Film (%)
(Average of 400 ~ 700nm) 99.8 99.8 99.7 99.8 Transmittance (%) of coating film (400nm) 99.7 99.7 99.5 99.7
Chemical resistance % Change in mix thickness 98 101 79 0 Transmittance change (%) 100 100 100 *) Adhesion 100 100 100 *)

*) It could not be measured because all of the coating films were dissolved in N-methylpyrrolidone by dipping.

From the result of Table 1, using the curable resin composition of this invention, it was confirmed that the coating film formed by hardening at 150 degreeC was excellent in chemical-resistance.

Curable resin composition of this invention can form the coating film excellent in chemical-resistance even if hardening temperature is less than 200 degreeC. As a result, it is especially useful as a member of a display apparatus using a plastic substrate.

Claims (6)

Curable property which contains following (A), (B), (C), (D) and (E), and content of (B) is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of content of (A). Resin composition.
(A) It is derived from the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, the structure which epoxidized unsaturated alicyclic hydrocarbon, and the monomer which has a carbon-carbon unsaturated double bond. A copolymer containing the structural unit to make, and whose acid value is 30 mg-KOH / g or more and 180 mg-KOH / g or less
(B) an epoxy resin having an acid value of less than 30 mg-KOH / g
(C) The compound which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group.
(D) thermal acid generator
(E) solvent The method of claim 1,
Curable resin whose structure which epoxidized unsaturated alicyclic hydrocarbon and the monomer which has a carbon-carbon unsaturated double bond are at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II). Composition.
[Formula 6]

[In formula (I) and formula (II), R <^1> and R <^2> respectively independently represents a hydrogen atom or C1-C? The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.
X ¹ and X ² are each independently a single bond or 1? The alkanediyl group of 6 is represented and -CH ₂ -contained in the alkanediyl may be substituted with -O-, -S-, or -NR ^3- . R ³ represents a hydrogen atom or 1? 4 represents an alkyl group] The method of claim 1,
Curable resin composition whose molecular weight of the compound which has 2 or more of at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group is 150 or more and 3000 or less. The coating film formed using the curable resin composition of Claim 1. The coating film which apply | coats the curable resin composition of Claim 1 to a board | substrate, and hardens | cures by heat and is formed. The display device containing the coating film of Claim 4.