TWI525113B - Hardened resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition.

In a liquid crystal display or the like, a curable resin composition is used in order to form an overcoat. As such a curable resin composition, for example, a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate and dipentaerythritol hexaacrylate are known. A curable resin composition of an ester and a solvent. Further, it is known that the curable resin composition is applied onto a substrate and baked at 220 ° C for 20 minutes to 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 has been expected. However, the heat resistant temperature of a general plastic substrate is only about 100 to 200 ° C (Non-Patent Document 1).

In addition, when the curable resin composition proposed in the prior art is cured at a low temperature of less than 200 ° C to form a coating film, the chemical resistance of the coating film formed may not be sufficient.

[Patent Document 1] JP-A-2009-149854

[Non-Patent Document 1] SHARP Technical Report, No. 85, pages 30 to 33, April 2003

[Problems to be solved by the invention]

The present invention provides the following [1] to [6].

[1] A curable resin composition containing the following (A), (B), (C), (D), and (E), and having a content of 100 parts by mass with respect to (A), (B) The content is 1 part by mass or more and 100 parts by mass or less;

(A) containing at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and a structure derived from epoxidation of unsaturated alicyclic hydrocarbons and carbon-carbon unsaturation a structural unit of a monomer of a double bond, a copolymer having an acid value of 30 mg-KOH/g or more and 180 mg-KOH/g or less

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

(C) a compound having at least one selected from the group consisting of a propylene fluorenyl group and a methacryl fluorenyl group

(D) Thermal acid generator

(E) Solvent.

[2] The curable resin composition according to the above [1], wherein the monomer having a structure for epoxidizing an unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is a compound represented by the formula (I) And at least one compound selected from the group consisting of the compounds represented by formula (II),

[Chemical 1]

[In the formulae (I) and (II), R ¹ and R ² are each independently represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ¹ and X; ^{2 is} independently shown as a single bond or an alkyldiyl group having 1 to 6 carbon atoms, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-, -S- or -NR ³ -, and R ^{3 is} shown as A hydrogen atom or an alkyl group having 1 to 4 carbon atoms].

[3] The curable resin composition according to the above [1] or [2], wherein the compound having at least one selected from the group consisting of a propylene group and a methacryl group is used. The molecular weight is 150 or more and 3,000 or less.

[4] A coating film formed by using the curable resin composition according to any one of the above [1] to [3].

[5] A coating film obtained by applying the curable resin composition according to any one of the above [1] to [3] to a substrate and curing by heat.

[6] A display device comprising the coating film of the above [4] or [5].

[Best form of implementing the invention]

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention contains the following (A), (B), (C), (D), and (E), and the content of (B) is 100 parts by mass based on the content of (A). It is a curable resin composition of 1 part by mass or more and 100 parts by mass or less.

(A) containing at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and a structure derived from epoxidation of unsaturated alicyclic hydrocarbons and carbon-carbon unsaturation The structural unit of the monomer of the double bond, and the copolymer having an acid value of 30 mg-KOH/g or more (hereinafter also referred to as "resin (A)").

(B) An epoxy resin having an acid value of less than 30 mg-KOH/g (hereinafter also referred to as "epoxy resin (B)").

(C) A compound having at least one selected from the group consisting of an acryloyl group and a methacryl group (hereinafter also referred to as "polymerizable compound (C)").

(D) Thermal acid generator

(E) solvent

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

The curable resin composition of the present invention contains the resin (A). The resin (A) is a structural unit containing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)") a copolymer with a structural unit derived from a monomer (b) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond (hereinafter also referred to as "(b)"), The acid value of the resin (A) is 30 mg-KOH/g or more and 180 mg-KOH/g or less.

The resin (A) used in the curable resin composition of the present invention may, for example, be

Resin (A2-1): a copolymer obtained by polymerizing (a) and (b), and

Resin (A2-2): (a), (b) and a monomer (c) copolymerizable with (a) and (b) (except that it does not have a structure for epoxidizing an unsaturated alicyclic hydrocarbon) (There is also a copolymer obtained by polymerization in the case of "(c)"), but the resin (A) is preferably a resin (A2-1).

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; Acid, fumaric acid, methyl maleic acid, methyl fumaric acid, methylene succinic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4, 5, 6 - an unsaturated dicarboxylic acid such as tetrahydrofurfuric acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid or 1,4-cyclohexene dicarboxylic acid; methyl-5- Decalene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]g a carboxylic acid-containing bicyclic unsaturated compound such as 2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, sub Methyl succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydroanthracene Anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norborne anhydride) Ydride)), etc., unsaturated dicarboxylic acid anhydride; succinic acid mono [2-(methyl) acrylonitrile oxyethyl] ester, decanoic acid mono [2-(methyl) propylene thioethyl ester] An unsaturated mono[(meth)acryloyloxyalkyl]ester of a polyvalent carboxylic acid having a valence of 2 or more; an unsaturated acrylic acid having a hydroxyl group and a carboxyl group in the same molecule as α-(hydroxymethyl)acrylic acid Esters and the like.

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

Here, in the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4- Epoxycyclohexyl methacrylate (for example, cyclomer A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; DAICEL Chemical Industry Co., Ltd.) And a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[Chemical 2]

In the formulae (I) and (II), R ¹ and R ² each independently 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 ¹ and X ² are each independently shown as a single bond or an alkyldiyl group having 1 to 6 carbon atoms, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-, -S- or -NR ³ -. R ³ is represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

As the hydroxyalkyl group in which a hydrogen atom may be substituted by a hydroxyl group, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

As R ¹ and R ² , for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

As the alkanediyl group, for example, methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5- Dibasic, hexane-1,6-diyl and the like.

As X ¹ and X ² , for example, a single bond, a methylene group, an exoethyl group, a *-CH ₂ -O- (* is shown to bond with an O) group, and *-CH ₂ CH ₂ -O are preferable. More preferably, for example, a single bond, a *-CH ₂ CH ₂ -O- group, and even more preferably, for example, a single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) is, for example, a compound represented by the formula (I-1) to the formula (I-15). Preferably, for example, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I- 15). More preferably, for example, the formula (I-1), the formula (I-7), the formula (I-9), and the formula (I-15).

[Chemical 3]

The compound represented by the formula (II) is, for example, a compound represented by the formula (II-1) to the formula (II-15). Preferably, for example, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II- 15). More preferably, for example, the formula (II-1), the formula (II-7), the formula (II-9), and the formula (II-15).

[Chemical 4]

The compound of the formula (I) and the compound of the formula (II) can be used alone. Also, these can be mixed at any ratio. When mixing, the mixing ratio is in molar ratio, and formula (I): formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20:80. 80:20.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl Alkyl (meth) acrylates such as alkyl (meth) acrylates; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (referred to as dicyclopentanyl (meth) acrylate as a conventional name in the art), dicyclopentyloxyethyl (methyl) a (meth)acrylic acid cyclic alkyl ester such as acrylate or isodecyl (meth) acrylate; (meth) acrylate, benzyl (meth) acrylate or the like (methyl) Aryl or aralkyl acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl methylene succinate; 2-hydroxyethyl a hydroxyalkyl ester such as (meth) acrylate or 2-hydroxypropyl (meth) acrylate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] g- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[ 2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5 -ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1] Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene , 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2 - alkene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxy) a bicyclic unsaturated compound of carbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl cis-butane Equinone imine, N-cyclohexyl maleimide, N-benzyl maleimide, N-butyl quinone imin-3-butylimide Acid ester, N-butyl diimide imino-4-butylimide butyl butyl ester, N-butyl diimide amide-6-butylene Dicarbonyl ruthenium such as quinoidimine hexanoate, N-butyl quinone imino-3-butylimide propionate, N-(9-acridinyl) maleimide Imine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, Vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene Wait.

As (c), in addition to the foregoing, for example, a monomer having a structure in which a chain olefin is epoxidized and a carbon-carbon unsaturated double bond, having an oxetanyl group and a carbon-carbon unsaturated double bond a monomer and a monomer having a tetrahydrofuranyl group and a carbon-carbon unsaturated double bond.

As the monomer having a structure in which a chain olefin is epoxidized and a carbon-carbon unsaturated double bond, specifically, for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-Methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-double (glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-double (shrinkage) Glyceryloxymethyl)styrene, 2,3,4-gins (glycidyloxymethyl)styrene, 2,3,5-gins (glycidyloxymethyl)styrene, 2,3,6 - ginseng (glycidyloxymethyl) styrene, 3,4,5-gin (glycidyloxymethyl)styrene, 2,4,6-glycol (glycidyloxymethyl)styrene, special The compound or the like described in JP-A-H07-248625.

As the monomer having an oxetanyl group and a carbon-carbon unsaturated double bond, for example, 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl- 3-propenyl methoxymethyl oxetane, 3-ethyl-3-methylpropenyl methoxymethyl oxetane, 3-ethyl-3-propenyl methoxymethyl oxalate Cyclobutane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3 - Methyl propylene decyl oxyethyl oxetane, 3-ethyl-3-propenyl oxy oxy oxetane, and the like.

Specific examples of the monomer having a tetrahydrofuranyl group and a carbon-carbon unsaturated double bond include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. .

Among these, as (c), cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, N-cyclohexyl pentene is preferable. Diimine and styrene.

In the resin (A2-1), the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the resin (A2-1) is preferably in the range below.

The structural unit derived from (a): 5 to 60 mol% (more preferably 10 to 50 mol%),

The structural unit derived from (b): 40 to 95 mol% (more preferably 50 to 90 mol%).

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

As the resin (A2-1), (b) is preferably a resin (A2-1) having a structure for epoxidizing a polycyclic unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond, (b) More preferably, it is a resin (A2-1) of at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II).

For the resin (A2-1), for example, the method described in the document "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972) Manufactured by references cited in the literature.

Specific examples include a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is substituted with nitrogen to deoxidize, stir, heat, and maintain the temperature. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and any of the fields can be generally used by users. For example, as a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) or the like) or an organic peroxide is mentioned. (Bestylene oxyhydroxide, etc.), as a solvent, as long as it can dissolve each monomer, as a solvent (E) of a curable resin composition, the solvent etc. which are mentioned later can be used.

Further, the obtained copolymer may be used as a solid (powder) by directly using the solution after the reaction, or using a solution which has been concentrated or diluted, or using a method such as reprecipitation. In particular, when the polymerization is carried out by using a solvent similar to the solvent (E) to be described later as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified.

In the resin (A2-2), the ratio of the structural unit derived from each monomer to the total number of moles of the entire structural unit constituting the resin (A2-2) is preferably in the range below.

The structural unit derived from (a): 2 to 55 mol% (more preferably 5 to 45 mol%),

The structural unit derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol%),

The structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%).

When the ratio of the structural unit of the resin (A2-2) is in the above range, the storage stability, solvent resistance, heat resistance, and surface hardness tend to be improved.

As the resin (A2-2), (b) is preferably a resin (A2-2) having a structure in which a polycyclic unsaturated alicyclic hydrocarbon is epoxidized and a monomer having a carbon-carbon unsaturated double bond, (b) More preferably, it is a resin (A2-2) of at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II).

The resin (A2-2) can be produced by the same method as the resin (A2-1).

Specific examples of the resin (A2-1) include (meth)acrylic acid/copolymer of the formula (I-1), (meth)acrylic acid/copolymer of the formula (I-2), and (meth)acrylic acid. / copolymer of the formula (I-3), (meth)acrylic acid / copolymer of the formula (I-4), (meth)acrylic acid / copolymer of the formula (I-5), (meth)acrylic acid / (I-6) copolymer, (meth)acrylic acid / copolymer of formula (I-7), (meth)acrylic acid / copolymer of formula (I-8), (meth)acrylic acid / formula (I -9) copolymer, (meth)acrylic acid / copolymer of formula (I-10), (meth)acrylic acid / copolymer of formula (I-11), (meth)acrylic acid / formula (I-12 Copolymer, (meth)acrylic acid / copolymer of formula (I-13), (meth)acrylic acid / copolymer of formula (I-14), (meth)acrylic acid / formula (I-15) Copolymer, (meth)acrylic acid / copolymer of formula (II-1), (meth)acrylic acid / copolymer of formula (II-2), copolymer of (meth)acrylic acid / formula (II-3) , (meth)acrylic acid / copolymer of the formula (II-4), (meth)acrylic acid / copolymer of the formula (II-5), (meth)acrylic acid / copolymer of the formula (II-6), a copolymer of methyl)acrylic acid/formula (II-7), a copolymer of (meth)acrylic acid/formula (II-8), Methyl)acrylic acid / copolymer of formula (II-9), (meth)acrylic acid / copolymer of formula (II-10), (meth)acrylic acid / copolymer of formula (II-11), (methyl Acrylic / copolymer of formula (II-12), (meth)acrylic acid / copolymer of formula (II-13), (meth)acrylic acid / copolymer of formula (II-14), (meth)acrylic acid / copolymer of formula (II-15), (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1), (meth)acrylic acid / formula (I-2) / formula (II -2) copolymer, (meth)acrylic acid / copolymer of formula (I-3) / formula (II-3), (meth)acrylic acid / formula (I-4) / formula (II-4) Copolymer, (meth)acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth)acrylic acid / copolymer of formula (I-6) / formula (II-6), Methyl)acrylic acid / copolymer of formula (I-7) / formula (II-7), (meth)acrylic acid / copolymer of formula (I-8) / formula (II-8), (meth)acrylic acid / copolymer of the formula (I-9) / formula (II-9), (meth)acrylic acid / copolymer of the formula (I-10) / formula (II-10), (meth)acrylic acid / formula (I -11) / copolymer of the formula (II-11), (meth)acrylic acid / copolymer of the formula (I-12) / formula (II-12), (meth)acrylic acid / formula (I-13) / Copolymer of formula (II-13), (meth)acrylic acid / formula (I-14) / (II-14) copolymer, (meth)acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth)acrylic acid / formula (I-1) / formula (I-7 Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / formula (I-2) Copolymer, crotonic acid / copolymer of formula (I-3), crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5), crotonic acid / formula (I- 6) copolymer, crotonic acid / copolymer of formula (I-7), crotonic acid / copolymer of formula (I-8), crotonic acid / copolymer of formula (I-9), crotonic acid / formula ( Copolymer of I-10), crotonic acid / copolymer of formula (I-11), crotonic acid / copolymer of formula (I-12), crotonic acid / copolymer of formula (I-13), crotonic acid / Copolymer of 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), croton Acid / copolymer of formula (II-3), crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6) , Crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / formula (II -10) copolymer, crotonic acid / copolymer of formula (II-11), crotonic acid / copolymer of formula (II-12), crotonic acid / copolymer of formula (II-13), crotonic acid / formula Copolymer of (II-14), crotonic acid / copolymer of formula (II-15), copolymer of maleic acid / formula (I-1), maleic acid / formula (I-2) Copolymer, maleic acid / copolymer of formula (I-3), copolymer of maleic acid / formula (I-4), copolymer of maleic acid / formula (I-5) a copolymer of maleic acid/formula (I-6), a copolymer of maleic acid/formula (I-7), a copolymer of maleic acid/formula (I-8), Maleic acid/copolymer of formula (I-9), copolymer of maleic acid/formula (I-10), copolymer of maleic acid/formula (I-11), cis-butane Etheric acid / copolymer of formula (I-12), copolymer of maleic acid / formula (I-13), copolymer of maleic acid / formula (I-14), maleic acid Acid / copolymer of formula (I-15), copolymer of maleic acid / formula (II-1), copolymer of maleic acid / formula (II-2), maleic acid / a copolymer of the formula (II-3), a copolymer of maleic acid / formula (II-4), a copolymer of maleic acid / formula (II-5), maleic acid / copolymer of formula (II-6), copolymer of maleic acid / formula (II-7), copolymer of maleic acid / formula (II-8), maleic acid / formula (II-9) copolymer, maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11), maleic acid / formula (II -12) copolymer, maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / formula (II-15 Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-2), Methyl)acrylic acid/maleic anhydride/copolymer of formula (I-3), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-4), (meth)acrylic acid/cis Butic anhydride/copolymer of formula (I-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-6), (meth)acrylic acid/maleic anhydride/formula Copolymer of (I-7), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/formula (I-9) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-10), (methyl) Acrylic acid/maleic anhydride/copolymer of formula (I-11), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-12), (meth)acrylic acid/methylenebutene Anhydride/copolymer of formula (I-13), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-14), (meth)acrylic acid/maleic anhydride/formula (I- 15) a copolymer, (meth)acrylic acid/maleic anhydride/copolymer of the formula (II-1), (meth)acrylic acid/maleic anhydride/copolymer of the formula (II-2), (Meth)acrylic acid/maleic anhydride/copolymer of formula (II-3), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-4), (meth)acrylic acid/ Maleic anhydride/copolymer of formula (II-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-6), (meth)acrylic acid/maleic anhydride/ Copolymer of the formula (II-7), (meth)acrylic acid/maleic anhydride/copolymer of the formula (II-8), (meth)acrylic acid/maleic anhydride/formula (II-9) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-11), (A) Acrylic/butylene Anhydride/copolymer of formula (II-12), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-13), (meth)acrylic acid/maleic anhydride/formula (II- 14) a copolymer, (meth)acrylic acid/maleic anhydride/copolymer of the formula (II-15), and the like.

Specific examples of the resin (A2-2) include (meth)acrylic acid/copolymer of the formula (I-1)/methyl(meth)acrylate, and (meth)acrylic acid/formula (I-2). /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-3) / methyl (meth) acrylate, (meth) acrylate / formula (I-4) /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-5) / methyl (meth) acrylate, (meth) acrylate / formula (I-6) /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-7) / methyl (meth) acrylate, (meth) acrylate / formula (I-8) /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-9) / methyl (meth) acrylate, (meth) acrylate / formula (I-10) /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-11) / methyl (meth) acrylate, (meth) acrylate / formula (I-12) /Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (I-13) / methyl (meth) acrylate, (meth) acrylate / formula (I-14) /Methyl (meth) acrylate copolymer, ( (meth)acrylic acid / copolymer of the formula (I-15) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-1) / methyl (meth) acrylate, ( (meth)acrylic acid / copolymer of the formula (II-2) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-3) / methyl (meth) acrylate, ( (meth)acrylic acid / copolymer of the formula (II-4) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of the formula (II-5) / methyl (meth) acrylate, ( (meth)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, ( Methyl)acrylic acid / formula (II-14) / Copolymer of (meth) acrylate, (meth)acrylic acid / copolymer of formula (II-15) / methyl (meth) acrylate, (meth) acrylate / formula (I-1) / two Copolymer of cyclopentyl (meth) acrylate, (meth)acrylic acid / copolymer of formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylate / formula ( I-1) / copolymer of formula (II-1) / dicyclopentanyl (meth) acrylate, copolymerization of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate , maleic acid / copolymer of formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I-1) / two Copolymer of cyclopentyl (meth) acrylate, copolymer of (meth) acrylate / (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate , Crotonic acid / copolymer of formula (II-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (II-1) / dicyclopentanyl (meth) acrylate Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/dicyclopentanyl (meth) acrylate, (meth)acrylic acid / formula (II-1) /Methyl (meth) acrylate / bicyclic Copolymer of alkyl (meth) acrylate, copolymer of (meth) acrylate / formula (I-1) / phenyl (meth) acrylate, (meth) acrylate / formula (II-1) / Copolymer of phenyl (meth) acrylate, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / formula (I -1) / copolymer of phenyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / cis-butene Diacid anhydride / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylate / formula (I-1) / methyl (meth) acrylate / phenyl (methyl) Acrylate copolymer, crotonic acid / copolymer of formula (II-1) / phenyl (meth) acrylate, maleic acid / formula (II-1) / phenyl (meth) acrylate Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/phenyl (meth) acrylate, (meth)acrylic acid / formula (II-1) / methyl ( Copolymer of methyl acrylate/phenyl (meth) acrylate, copolymer of (meth) acrylate / diethyl ether of formula (I-1) / maleic acid, (meth)acrylic acid / (II-1) / diethyl maleate Polymer, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / formula (I-1) / maleic acid Copolymer of diethyl 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 formula (I-1) / methyl (meth) acrylate / diethyl maleate, crotonic acid / Copolymer of formula (II-1) / diethyl maleate, copolymer of maleic acid / diethyl ether of formula (II-1) / maleic acid, (meth)acrylic acid / Maleic anhydride / copolymer of formula (II-1) / diethyl maleate, (meth)acrylic acid / formula (II-1) / methyl (meth) acrylate / cis-butene Copolymer of diethyl diacid, copolymer of (meth)acrylic acid / formula (I-1)/2-hydroxyethyl (meth) acrylate, (meth)acrylic acid / formula (II-1) / a copolymer of 2-hydroxyethyl (meth) acrylate, a copolymer of (meth)acrylic acid / formula (I-1) / formula (II-1)/2-hydroxyethyl (meth) acrylate, Crotonic acid/copolymer of formula (I-1)/2-hydroxyethyl (meth) acrylate, Butic acid/copolymer of formula (I-1)/2-hydroxyethyl (meth) acrylate, (meth)acrylic acid/maleic anhydride/formula (I-1)/2-hydroxyl Copolymer of (meth) acrylate, (meth)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid Copolymer of formula (II-1)/2-hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (II-1)/2-hydroxyethyl (meth) acrylate (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/2-hydroxyethyl (meth) acrylate, (meth)acrylic acid / formula (II-1) / methyl group a copolymer of (meth) acrylate/2-hydroxyethyl (meth) acrylate, a copolymer of (meth) acrylate / formula (I-1) / bicyclo [2.2.1] hept-2-ene, (Meth)acrylic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (I-1) / formula (II-1) / bicyclo [ 2.2.1] copolymer of hept-2-ene, crotonic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (I-1) /bicyclo[2.2.1]Hept-2-ene copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1)/bicyclo[2.2.1]heptan-2- Copolymer of alkene, (meth)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula (II-1 / bicyclo [2.2.1] copolymer of hept-2-ene, maleic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid /maleic anhydride / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (II-1) / methyl (meth) acrylate /Bicyclo[2.2.1]Hept-2-ene copolymer, (meth)acrylic acid / copolymer of formula (I-1) / N-cyclohexylmethylene iodide, (meth)acrylic acid / Copolymer of formula (II-1)/N-cyclohexylmethyleneimine, (meth)acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylbutene Copolymer of quinone imine, crotonic acid / copolymer of formula (I-1) / N-cyclohexyl maleimide, maleic acid / formula (I-1) / N-cyclohexyl cis Copolymer of butylenediimide, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/N-cyclohexylmethyleneimine, (meth)acrylic acid/ Copolymer of the formula (I-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, crotonic acid / formula (II-1) / N-cyclohexane Copolymer of maleimide, copolymer of maleic acid/(II-1)/N-cyclohexylmethyleneimine, (meth)acrylic acid/maleic anhydride / (II-1) / N-cyclohexyl maleimide copolymer, (meth) acrylic acid / (II-1) / methyl (meth) acrylate / N-cyclohexyl cis Copolymer of butylenediimide, (meth)acrylic acid/copolymer of formula (I-1)/styrene, (meth)acrylic acid/copolymer of formula (II-1)/styrene, (a) Acrylic acid / copolymer of formula (I-1) / formula (II-1) / styrene, crotonic acid / copolymer of formula (I-1) / styrene, maleic acid / formula (I- 1) / copolymer of styrene, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1) / styrene, (meth)acrylic acid / formula (I-1) / methyl ( Copolymer of methyl acrylate/styrene, copolymer of crotonic acid / formula (II-1) / styrene, copolymer of maleic acid / formula (II-1) / styrene, (methyl Acrylic acid/maleic anhydride/copolymer of formula (II-1)/styrene, (meth)acrylic acid/copolymer of formula (II-1)/methyl(meth)acrylate/styrene, (meth)acrylic acid / formula (I-1) / N-cyclohexyl cis-butyl Copolymer of bis-imine/styrene, copolymer of (meth)acrylic acid/(II-1)/N-cyclohexylmethyleneimine/styrene, (meth)acrylic acid/form ( I-1) / (II-1) / N-cyclohexyl maleimide / styrene copolymer, crotonic acid / formula (I-1) / N-cyclohexyl maleicene Amine/styrene copolymer, maleic acid/copolymer of formula (I-1)/N-cyclohexylmethyleneimine/styrene, (meth)acrylic acid/maleic anhydride / (I-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / (I-1) / methyl (meth) acrylate / N- Copolymer of cyclohexylmethylene iodide/styrene, crotonic acid / copolymer of formula (II-1) / N-cyclohexylmethylene iodide / styrene, maleic acid / Copolymer of formula (II-1)/N-cyclohexylmethyleneimine/styrene, (meth)acrylic acid/maleic anhydride/formula (II-1)/N-cyclohexyl cis-butyl Copolymer of enediamine/styrene, copolymerization of (meth)acrylic acid/(II-1)/methyl(meth)acrylate/N-cyclohexylmaleimide/styrene Things and so on.

The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 6,000 to 15,000. When the weight average molecular weight of the resin (A) is in the above range, the coatability tends to be good, and film formation is less likely to occur during development, and the release property of the non-pixel portion during development is good. tendency.

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, still more preferably from 1.5 to 3.0, still more preferably 1.8. ~2.8. When the molecular weight distribution is in the above range, the developability tends to be excellent.

The acid value of the resin (A) is 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more, 150 mg-KOH/g or less, and still more preferably 50 mg-KOH/g or more. 135 mg-KOH/g or less. Here, the acid value is determined by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A), and can be determined by titration with 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 to 90% by mass, more preferably 40 to 80% by mass, particularly preferably 40 to 70% by mass based on the total amount of the resin (A) and the polymerizable compound (C). %. When the content of the resin (A) is in the above range, the chemical resistance tends to be good.

The curable resin composition of the present invention contains an epoxy resin (B) having an acid value of less than 30 mg-KOH/g. The acid value of the epoxy resin (B) is preferably 20 mg-KOH/g or less, more preferably 10 mg-KOH/g or less. Here, the term "epoxy resin" means a compound having two or more oxirane groups, or a mixture thereof, and is not limited to a polymer compound. The epoxy group (B) has an oxirane group, preferably a structure in which a chain olefin is epoxidized.

Examples of the epoxy resin (B) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolac type epoxy resin. Commercial products of these types can also be used. Examples of commercially available bisphenol A type epoxy resins include Epikote 828, 1001, 1002, 1003, 1004, 1007, 1009, 1010 (above, Mitsubishi Chemical Corporation). Examples of the commercially available bisphenol F-type epoxy resin include Epikote 807 and 834 (above, manufactured by Mitsubishi Chemical Corporation). Examples of the commercially available phenol novolak type epoxy resin include Epikote 152, 154, 157H65 (above, Mitsubishi Chemical Corporation), EPPN201, and 202 (above, manufactured by Nippon Kayaku Co., Ltd.). As a commercially available cresol novolac type epoxy resin, for example, Sumi-epoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN- 1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epikote 180S75 (Mitsubishi Chemical Co., Ltd.), etc.

Further, as the epoxy resin which is commercially available, for example, CY175, CY177, CY179 (above, manufactured by ASAHI KASEI E-materials), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (for example) The above, UCC company), show (transliteration) 509 (Showa Denko (share) system), Araldite CY-182, with CY-192, with CY-184 (above, ASAHI KASEI E-materials), Epiclon 200 , such as 400 (above, DIC (share)), Epikote 871, 872, EP1032H60 (above, Mitsubishi Chemical Co., Ltd.) and other cyclic aliphatic epoxy resins; Epikote 190P, same as 191P (above, Mitsubishi Chemical) (Shares) aliphatic fatty glycidyl ethers such as Epolite 100MF (manufactured by Kyoei Chemical Co., Ltd.) and EPIOL TMP (manufactured by Nippon Oil & Fats Co., Ltd.).

Among them, as the epoxy resin (B), a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolac type epoxy resin are preferable.

The content of the epoxy resin (B) is 1 part by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 100 parts by mass or less based on 100 parts by mass of the resin (A). 5 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 25 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less.

When the content of the epoxy resin (B) is within the above range, the obtained coating film tends to have excellent flatness.

The curable resin composition of the present invention contains a polymerizable compound (C) having at least one selected from the group consisting of a propylene group and a methacryl group. The molecular weight of the polymerizable compound (C) is preferably 150 or more and 3,000 or less, more preferably 200 or more and 1,500 or less. When two or more polymerizable compounds (C) are contained, the weight average molecular weight of the mixture is preferably in the above range.

Examples of the compound having at least one selected from the group consisting of an acryloyl group and a methacryl group include 1,6-hexanediol di(meth)acrylate and ethylene glycol. Di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether, 3-methyl Pentyl diol di(meth) acrylate or the like.

Examples of the compound having at least one selected from the group consisting of a propylene group and a methacryl group include, for example, trimethylolpropane tri(meth)acrylate, neopentyl alcohol (Meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl alcohol Reaction of (meth) acrylate with an acid anhydride, reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, caprolactone denatured pentaerythritol tetra (meth) acrylate, caprolactone denaturation Dipentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, ethylene oxide denatured pentaerythritol tetra (meth) acrylate, ethylene oxide denature Pentaerythritol penta (meth) acrylate, ethylene oxide-denatured neopentyltetraol hexa(meth) acrylate, propylene oxide-denatured neopentyltetrakis (meth) acrylate, propylene oxide-denatured dipentaerythritol Penta(meth)acrylate, propylene oxide, dipentaerythritol hexa(meth)acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a compound having at least one selected from the group consisting of a propylene group and a methacryl group, and more preferably a trimethylolpropane. Tris(meth)acrylate and dipentaerythritol hexa(meth)acrylate. When the polymerizable compound (C) is a compound such as this, the obtained coating film tends to have excellent chemical resistance.

To the extent that the effects of the present invention are not impaired, a compound having at least one selected from the group consisting of an acryloyl group and a methacryl group can be used in combination.

As such a compound, for example, (a), (b), (c), nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl group constituting the monomer of the resin (A) Acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like.

The content of the polymerizable compound (C) is preferably from 10 to 60% by mass, more preferably from 20 to 60% by mass, even more preferably from 30 to 60% by mass, based on the total amount of the resin (A) and the polymerizable compound (C). 60% by mass. When the content of the polymerizable compound (C) is within the above range, the coating film tends to be excellent in strength, smoothness, and reliability.

The curable resin composition of the present invention contains a thermal acid generator (D). The thermal acid generator is a compound which generates an acid by the action of heat. It is preferably a compound which can generate an acid below the post-baking temperature which will be described later.

Examples of the thermal acid generator (D) include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts.

As the above sulfonium salt, for example, (4-hydroxyphenyl) dimethyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (2-methylbenzyl) methyl hydrazine (Trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)benzylmethyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (4-methylbenzyl) Methyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)(1-naphthylmethyl)methyl bis(trifluoromethanesulfonyl) quinone imine, 4-methoxycarbonyloxyphenyl)dimethylindole bis(trifluoromethanesulfonyl) quinone imine, (4-methoxycarbonyloxyphenyl)benzylmethylhydrazine bis(trifluoromethanesulfonate) (i) quinone imine, (4-methoxycarbonyloxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine, (4-methoxycarbonyloxybenzene (4-methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxyphenyl)benzylmethyl bis(trifluoromethanesulfonyl)醯iamine, (4-acetoxyphenyl) (4-methylbenzyl)methyl bis(trifluoromethanesulfonyl) ruthenium, (4-ethyloxyphenyl) (2 -methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxy) Phenyl) dimethyl bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxyphenyl) (1-naphthylmethyl)methyl hydrazine bis(trifluoromethanesulfonyl)醯imine; (4-hydroxyphenyl) dimethyl hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl) methyl sulfonium hexafluorophosphate, (4-hydroxyphenyl) Benzylmethylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(4-methylbenzyl)methylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(1-naphthylmethyl)methyl Based on hexafluorophosphate, (4-acetoxyphenyl) dimethyl sulfonium hexafluorophosphate, (4-acetoxyphenyl)benzylmethyl hexafluorophosphate, (4-B (醯-Oxylphenyl)(2-methylbenzyl)methylphosphonium hexafluorophosphate, (4-acetoxyphenyl)(4-methylbenzyl)methylphosphonium hexafluorophosphate, (4 -(ethoxyphenyl)(1-naphthylmethyl)methylphosphonium hexafluorophosphate; (4-hydroxyphenyl)dimethyltrifluoromethanesulfonate, (4-hydroxyphenyl) 2-methylbenzyl)methylindole trifluoromethanesulfonate, (4-hydroxyphenyl)benzylmethylphosphonium trifluoromethanesulfonate, (4-hydroxyphenyl) (4-methylbenzyl) Methyl fluorene trifluoromethane sulfonate, (4-hydroxyphenyl) (1-naphthylmethyl) methyl hydrazine Fluoromethanesulfonate, (4-acetoxyphenyl)dimethylhydrazinetrifluoromethanesulfonate, (4-acetoxyphenyl)benzylmethylsulfonium trifluoromethanesulfonate, 4-Ethyloxyphenyl)(2-methylbenzyl)methylindole trifluoromethanesulfonate, (4-ethoxymethoxyphenyl)(4-methylbenzyl)methylfluorene Methanesulfonate, (4-acetoxyphenyl)(1-naphthylmethyl)methylsulfonium trifluoromethanesulfonate; (4-ethylhydrazinophenyl)dimethylsulfonium hexafluoroantimonate Salt, (4-benzyloxycarbonyloxyphenyl)dimethylhydrazine hexafluoroantimonate, (4-benzylideneoxyphenyl)dimethylsulfonium hexafluoroantimonate, (3-chloro-4) -(ethoxyphenyl)dimethyl hexafluoroantimonate, (4-hydroxyphenyl)benzylmethylphosphonium hexafluoroantimonate, (4-acetoxyphenyl)benzylmethyl Hexafluoroantimonate, (4-methoxyphenyl)benzylmethylphosphonium hexafluoroantimonate, (4-hydroxy-2-methylphenyl)benzylmethylphosphonium hexafluoroantimonate, (4-hydroxyphenyl) bisbenzyl hexafluoroantimonate, (4-ethoxymethoxyphenyl) bisbenzyl hexafluoroantimonate, (4-methoxyphenyl) bisbenzyl hydrazine Hexafluoroantimonate, (4-hydroxy-3-tert-butyl-5-methylphenyl) bisbenzyl hexafluoroantimonate (4-hydroxyphenyl)(4-chlorobenzyl)methylhydrazine hexafluoroantimonate, (4-hydroxyphenyl)(4-nitrobenzyl)methylphosphonium hexafluoroantimonate, (4 -hydroxy-3-methylphenyl)(4-nitrobenzyl)methylphosphonium hexafluoroantimonate, (4-hydroxyphenyl)(3,5-dichlorobenzyl)methylphosphonium hexafluoroantimony Acid salt, (4-hydroxy-3-chlorophenyl)(2-chlorobenzyl)methylphosphonium hexafluoroantimonate; (4-acetoxyphenyl)dimethylhydrazine hexafluoroarsenate, (4-Benzyldecyloxyphenyl)dimethylsulfonium hexafluoroarsenate, (3-chloro-4-hydroxyphenyl)benzylmethylphosphonium hexafluoroarsenate, (3-chloro-4- Hydroxyphenyl) bisbenzylphosphonium hexafluoroarsenate; (4-hydroxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(4-methoxybenzyl)methylhydrazine Hexafluorophosphate, (4-hydroxyphenyl) bisbenzylphosphonium hexafluorophosphate, (4-hydroxyphenyl) (4-methoxybenzyl)benzylphosphonium hexafluorophosphate, (4-hydroxybenzene) (4-chlorobenzyl)methylphosphonium hexafluorophosphate or the like.

As the aforementioned benzothiazolium salt, for example, 3-benzylbenzothiazolium hexafluoroantimonate, 3-(4-methoxybenzyl)benzothiazolium hexafluoroantimonate, 2-methyl Sulfhydryl-3-benzylbenzothiazolium hexafluoroantimonate, 5-chloro-3-benzylbenzothiazolium hexafluoroantimonate; 3-benzylbenzothiazolium hexafluorophosphate; - Benzylbenzothiazolium tetrafluoroborate or the like.

Among them, as the thermal acid generator (D), a phosphonium salt and a benzothiazolium salt are preferred, and a sulfonium salt is more preferred, and (4-hydroxyphenyl)benzylmethylguanidine bis (three) is more preferred. Fluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (4 -methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)(1-naphthylmethyl)methylhydrazine bis(trifluoromethanesulfonyl)anthracene Imine, (4-acetoxyphenyl) dimethyl bis(trifluoromethanesulfonyl) ruthenium, (4-hydroxyphenyl)benzylmethyl bis (trifluoromethanesulfonyl)醯imino, (4-acetoxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) ruthenium, (4-ethyloxyphenyl) 4-methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxyphenyl)(1-naphthylmethyl)methylhydrazine bis(trifluoromethanesulfonate) (醯) 醯 imine; (4-hydroxyphenyl)benzylmethyl hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl)methyl sulfonium hexafluorophosphate, (4- Hydroxyphenyl)(4-methylbenzyl)methylphosphonium hexafluorophosphate, (4-hydroxyphenyl) (1-naphthalene) Methyl)methylphosphonium hexafluorophosphate, (4-acetoxyphenyl)dimethyltrifluoromethanesulfonate, (4-acetoxyphenyl)benzylmethylphosphonium hexafluorophosphate Salt, (4-acetoxyphenyl) (2-methylbenzyl)methyl sulfonium hexafluorophosphate, (4-acetoxyphenyl) (4-methylbenzyl) methyl fluorene Fluorophosphate, (4-acetoxyphenyl)(1-naphthylmethyl)methylphosphonium hexafluorophosphate; (4-hydroxyphenyl)dimethyltrifluoromethanesulfonate, (4 -hydroxyphenyl)benzylmethylindole trifluoromethanesulfonate, (4-hydroxyphenyl)(2-methylbenzyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) ( 4-methylbenzyl)methylindole trifluoromethanesulfonate, (4-hydroxyphenyl)(1-naphthylmethyl)methylsulfonium trifluoromethanesulfonate, (4-acetoxybenzene) Benzylmethyl fluorene trifluoromethane sulfonate, (4-ethoxymethoxyphenyl) (2-methylbenzyl)methyl fluorene trifluoromethane sulfonate, (4-acetoxybenzene) (4-methylbenzyl)methylindole trifluoromethanesulfonate, (4-acetoxyphenyl)(1-naphthylmethyl)methylsulfonium trifluoromethanesulfonate; (4 -hydroxyphenyl)benzylmethylphosphonium hexafluoroantimonate, (4-hydroxyphenyl) bisbenzyl fluorene a group of fluoroantimonate, (4-acetoxyphenyl)benzylmethylphosphonium hexafluoroantimonate and (4-acetoxyphenyl)bisbenzylphosphonium hexafluoroantimonate Choose at least one of them.

As the thermal acid generator (D), it is also possible to use san-aid SI-250, the same SI-L85, the same SI-L110, the same SI-L145, the same SI-L150, the same SI-L160 (Sanxin Chemical Industry Co., Ltd. ()), etc., commercially available products.

The content of the thermal acid generator (D) is preferably 0.1 parts by mass or more, 10 parts by mass or less, more preferably 0.1 parts by mass, based on 100 parts by mass of the total of the resin (A) and the polymerizable compound (C). Above 5 parts by mass or less. When the content of the thermal acid generator (D) is in the above range, the visible light transmittance of the coating film tends to be high.

The curable resin composition of the present 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, an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), and a ketone solvent other than an ester solvent (Selected as a solvent containing -CO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, or the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acid, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetate Ester, cyclohexanol acetate, γ-butyrolactone, and the like.

As the ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol 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, phenethyl ether, methyl anisole, and the like.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid 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-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and the like.

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

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

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

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

These solvents may be used singly or in combination of two or more.

Among the above solvents, in terms of coatability and drying property, an organic solvent having a boiling point of 1 atm of 100 ° C or more and 200 ° C or less is preferable, and more preferably propylene glycol monomethyl ether or propylene glycol monomethyl acrylate. Ethyl ether acetate, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate and 3-methoxy-1-butanol The solvent selected from at least one of the groups is more preferably a solvent formed from at least one selected from the group.

The content of the solvent (E) in the curable resin composition of the present invention is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, even more preferably the total amount of the curable resin composition. 55 to 85% by mass. In other words, the solid content of the curable resin composition is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, still more preferably from 15 to 45% by mass. Here, the solid content means an amount obtained by removing the solvent (E) from the curable resin composition. When the content of the solvent (E) is within the above range, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater or a curtain flow coater), When coating is applied by a coating device such as an injection or a roll coater, the coating property is excellent.

The curable resin composition of the present invention may further contain an additive such as a filler, another polymer compound, an adhesion promoter, a thermal radical generator, an ultraviolet absorber, or a chain transfer agent, as needed.

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

Examples of the other polymer compound include a thermosetting resin such as a maleimide resin, a polyvinyl alcohol, a polyacrylic acid, a polyethylene glycol monoalkyl ether, a polyfluoroalkyl acrylate, and a polyester. A thermoplastic resin such as polyurethane or the like.

As the adhesion promoter, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-shrinkage Glyceryloxypropyltrimethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-sulfonylpropyltrimethoxydecane, and the like.

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 alkoxydiphenylketone.

Further, as the coagulant, for example, sodium polyacrylate or the like is specifically mentioned.

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

The curable resin composition of the present invention preferably contains a surfactant (F). Examples of the surfactant include a polyfluorene-based surfactant, a fluorine-based surfactant, a polyfluorene-based surfactant having a fluorine atom, and the like.

As the polyoxymethylene surfactant, for example, a surfactant having a decane bond is used.

Specifically, for example, Toray Silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the polyether modified polyoxygenated oil SH8400 (trade name: Dow 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 Co., Ltd.) and the like.

The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain. Specifically, for example, Fluorinert (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC) System), F-Top (registered trademark) EF301, with EF303, with EF351, with EF352 (Mitsubishi Materials Electronic Chemical Co., Ltd.), Surflon (registered trademark) S381, with S382, with SC101, with SC105 (Asahi Glass) )), E5844 (manufactured by Daikin Fine Chemical Research Institute).

The polyfluorene-based surfactant having a fluorine atom is, for example, a surfactant having a decane bond and a fluorocarbon chain. Specifically, for example, MEGAFACE (registered trademark) R08, the same BL20, the same F475, the same F477, the same F443 (DIC system), and the like. For example, MEGAFACE (registered trademark) F475 is preferred.

The content of the surfactant (F) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more, 0.1% by mass or less, and more preferably 0.01% by mass or more based on the curable resin composition. 0.05% by mass or less. The flatness of the coating film can be improved by containing the surfactant in the above range.

The curable resin composition of the present invention is substantially a coloring agent containing no pigment or dye. In the curable resin composition of the present invention, the content of the coloring agent with respect to the entire composition is, for example, preferably less than 1% by mass, more preferably less than 0.5% by mass.

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

In the curable resin composition of the present invention, when the coating film is formed, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. The average transmittance is a coating film having a thickness of 2 μm after heat curing (for example, 120 to 240° C. for 10 minutes to 120 minutes), and is measured by using a spectrophotometer at a measurement wavelength of 400 to 700 nm. value. Thereby, a coating film excellent in transparency in the visible light region can be provided.

The coating film of the present invention can be obtained by applying the curable resin composition of the present invention to a substrate and hardening it by heat.

Examples of the substrate include glass, metal, plastic, and the like, and a color filter, various insulating films, conductive films, and driving circuits may be formed on the substrate. Since the curable resin composition of the present invention can be cured at a temperature of 200 ° C or lower, a coating film can be formed on a substrate having a low heat resistance such as plastic.

The curable resin composition of the present invention can be applied to a substrate by using a spin coater, a slit/rotary coater, a slit coater, an injection, a roll coater, a dip coater, and the like. The coating device is used to carry out.

After coating, vacuum drying or prebaking, it is preferred to remove volatile components such as a solvent.

The coating film can be formed by baking the volatile film with the coating film which has been removed at 120 to 240 ° C for 10 to 120 minutes.

The film thickness of the coating film formed by the curable resin composition of the present invention is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like. For example, 0.1 to 10 μm.

According to the present invention, even when the curing temperature is less than 200 ° C, a coating film excellent in chemical resistance can be formed.

The coating film thus obtained is useful as an overcoat used for, for example, a liquid crystal display device or an electronic paper. Moreover, it can also be used for a display device such as a touch panel. Therefore, a display device having a high-quality coating film can be produced at a high yield.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The "%" and "parts" in the examples are % by mass and parts by mass without special notice.

(Synthesis Example 1)

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to prepare a nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was placed, and the mixture was heated to 70 ° C while stirring. Next, 40 parts of methacrylic acid, and a mixture of the monomer (I-1) and the monomer (II-1) {monomer ratio of the monomer (I-1): monomer (II-1) in the mixture = 50:50} 360 parts, dissolved in 190 parts of diethylene glycol ethyl methyl ether to prepare a solution, which was taken for 4 hours using a dropping pump, and dropped into a flask maintained at a temperature of 70 °C.

[Chemical 5]

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethyl methyl ether, and this solution was used for another. The drip pump took 5 hours to drip into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 42.3%. The obtained resin Aa had a weight average molecular weight (Mw) of 8,000, a molecular weight distribution (Mw/Mn) of 1.91, and an acid value of 60 mg-KOH/g.

(Synthesis Example 2)

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to prepare a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl group were placed. 105 parts by mass of the acetoxyacetate was heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid, and a mixture of the monomer (I-1) and the monomer (II-1) {monomer ratio of the monomer (I-1): monomer (II-1) in the mixture = 50:50} 240 parts, dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, which was taken for 4 hours using a dropping pump, and dropped into a flask maintained at a temperature of 70 °C.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate, and this solution was used. The drip pump took 4 hours to drip into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 32.6%. The obtained resin Ab had a weight average molecular weight (Mw) of 13,400, a molecular weight distribution (Mw/Mn) of 2.50, and an acid value of 113.9 mg-KOH/g.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin Aa and resin Ab was measured by the following conditions using the GPC method.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

[Example 1]

The polymerizable compound (C): trimethylolpropane triacrylate (A-TMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.) was mixed with 142 parts of the solution of the resin Aa obtained in Synthesis Example 1 (60 parts in terms of solid content). Molecular weight: 296) 40 parts, resin (B): o-cresol novolac type epoxy resin (Sumi-epoxy ESCN-195XL-80; manufactured by Sumitomo Chemical Co., Ltd., acid value: 0.1 mg-KOH/g), 10 parts, Thermal acid generator (D): (4-hydroxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine (SI-250; Sanxin Chemical Co., Ltd.) 0.5 parts, 1,3,5-gin (4-hydroxy-3,5-di-tert-butylbenzyl)-1,3,5-triazine -2,4,6 (1H,3H,5H)-trione (IRGANOX 3114; manufactured by Ciba Japan Co., Ltd.) 1.0 part and solvent (E), and the curable resin composition 1 was obtained. The solvent has a mass ratio of propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and diethylene glycol ethyl methyl ether to 20:20:60, and is a curable resin composition. The solid content of 1 was mixed as in 17.7%.

[Embodiment 2]

In addition to replacing the trimethylolpropane triacrylate with dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Chemical Co., Ltd., molecular weight: 578), 1,3,5-para (4-hydroxy-) 3,5-di-tert-butylbenzyl)-1,3,5-triazine The curable resin composition 2 was obtained in the same manner as in Example 1 except that -2,4,6 (1H,3H,5H)-trione.

[Example 3]

The curable resin composition 3 was obtained in the same manner as in Example 1 except that trimethylolpropane triacrylate was replaced by dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Chemical Co., Ltd.).

[Comparative Example 1]

In 184 parts of the resin solution containing the resin Ab obtained in Synthesis Example 2 (60 parts in solid content), dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 1, 3, 5- was mixed. Reference (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione (IRGANOX3114; Ciba Japan 0.8 parts of a solvent and a solvent were obtained, 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 14 20:33:33, and the solid content of the curable resin composition 4 was mixed as 17.7%.

<Average transmittance of the composition>

For the obtained curable resin composition, an ultraviolet visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) was used, and the average was measured at 400 to 700 nm. Transmittance (%). The results are shown in Table 1.

<Production of coating film>

A 2-square glass substrate (Eagle 2000; manufactured by Corning Co., Ltd.) was washed with a neutral detergent, water, and 2-propanol, followed by drying. The curable resin composition was spin-coated on the glass substrate, and prebaked at 100 ° C for 3 minutes, and then baked at 150 ° C for 60 minutes. After cooling, the film thickness of this coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.0 μm.

<Transmission rate measurement>

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

<Chemical resistance>

The obtained coating film was immersed in N-methylpyrrolidone at 30 ° C for 30 minutes, and the film thickness and transmittance before and after the immersion were measured, and the film thickness change (%) and the transmittance change (%) were determined according to the following formula. ). Both are the same, and the closer to 100%, the smaller the change before and after the immersion. When the film thickness change (%) is closer to 100%, it is preferable because the film is dissolved or swollen. When the transmittance change (%) is closer to 100%, the color or discoloration of the coating film is small, which is preferable.

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

Transmittance change (%): (transmission rate after immersion (%) / transmittance before immersion (%)) × 100

Moreover, the adhesion test was performed about the coating film after immersion. Using a blade and a super-tool guide (made by Taisho Machinery Co., Ltd.), a cut mark was placed on the coating film after the immersion at intervals of 1 mm, and 100 squares of 1 mm × 1 mm were produced. Next, a scotch tape (registered trademark) of 24 mm width (manufactured by Nichiban Co., Ltd.) was attached to the cut square of the coating film, and rubbed with an eraser from above the scotch tape to adhere the scotch tape to the coating film. After that, the end portion of the transparent adhesive tape was held after 2 minutes, and the film was peeled off in one go while maintaining a right angle with the coating film surface. Thereafter, the coating film was visually counted as the number of squares remaining on the substrate without being peeled off. The more the number of squares remaining on the substrate, the better the adhesion.

From the results of Table 1, it was confirmed that the curable resin composition of the present invention is a coating film formed by curing at 150 ° C, and is excellent in chemical resistance.

Industrial utilization

The curable resin composition of the present invention can form a coating film excellent in chemical resistance even when the curing temperature is less than 200 °C. Therefore, it is also useful particularly as a member of a display device using a plastic substrate.

Claims (5)

A curable resin composition containing the following (A), (B), (C), (D), and (E), and the content of (B) is 100 parts by mass based on the content of (A) 1 part by mass or more and 100 parts by mass or less; (A) containing at least one structural unit selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride and derived from having an unsaturated alicyclic ring a structural unit of a hydrocarbon epoxidation structure and a monomer of a carbon-carbon unsaturated double bond, wherein the monomer having a structure for epoxidizing an unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is a formula (I) a compound of at least one selected from the group consisting of a compound represented by the formula (II) and a copolymer having an acid value of 30 mg-KOH/g or more and 180 mg-KOH/g or less (B). The epoxy resin (C) having less than 30 mg-KOH/g has at least one compound (D) of a thermal acid generator having at least one selected from the group consisting of an acryloyl group and a methacryl group. E) Solvent [In the formulae (I) and (II), R ¹ and R ² are each independently represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ¹ and X; ^{2 is} independently shown as a single bond or an alkyldiyl group having 1 to 6 carbon atoms, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-, -S- or -NR ³ -, and R ^{3 is} shown as A hydrogen atom or an alkyl group having 1 to 4 carbon atoms]. The curable resin composition of the first aspect of the invention, wherein the compound having at least one selected from the group consisting of two groups of acryloyl group and methacryl fluorenyl group has a molecular weight of 150 or more. 3000 or less. A coating film formed by using a curable resin composition as in the first aspect of the patent application. A coating film which is formed by applying a curable resin composition as in the first aspect of the patent application to a substrate and hardening by heat. A display device comprising a coating film as in item 3 of the patent application.