KR101946646B1 - Curable resin composition - Google Patents

Abstract

[식 (1) 중, R¹ 은 벤질기 또는 탄소수 2 ∼ 5 의 시아노알킬기를 나타내고,
R² ∼ R⁴ 는 서로 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 ∼ 20 의 알킬기, 페닐기, 니트로기 또는 탄소수 1 ∼ 20 의 아실기를 나타내고, 그 알킬기 및 그 페닐기에 함유되는 수소 원자는 하이드록시기로 치환되어 있어도 된다]
을 함유하는 경화성 수지 조성물.(assignment)
A coating film excellent in heat resistance and a curable resin composition capable of forming a pattern.
(Solution)
(A) an addition polymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from an unsaturated compound having an oxiranyl group,
(B) a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group,
(C) a polymerization initiator, and
(D) a compound represented by the formula (1)

[In the formula (1), R ¹ represents a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms,
R ² to R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the hydrogen atom contained in the alkyl group and the phenyl group is a hydroxy group Which may be substituted]
Based on the weight of the curable resin composition.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition.

In a liquid crystal display or the like, a coating film such as a color filter protective film is used as a member. The color filter protective film is a coating film used to protect the color filter or the like from the chemical solution used for flattening the unevenness of the surface of the color filter or the black matrix formed as the underlayer . A curable resin composition is used to form a color filter protective film.

As such a curable resin composition, for example, a curable resin composition containing a copolymer of an unsaturated carboxylic acid and an aliphatic polycyclic epoxy compound, dipentaerythritol hexaacrylate and a polymerization initiator is known (Patent Document 1).

Japanese Laid-Open Patent Publication No. 2010-152335

The coating film or pattern formed using the curable resin composition known in the prior art is not always sufficiently high in heat resistance and may be easily colored by heat treatment.

The present invention provides the following [1] to [4].

[1] A curable resin composition comprising (A), (B), (C) and (D)

(A) an addition polymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a structural unit derived from an unsaturated compound having an oxiranyl group

(B) a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group

(C) Polymerization initiator

(D) a compound represented by the formula (1)

[Chemical Formula 1]

[In the formula (1), R ¹ represents a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms,

R ² to R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the hydrogen atom contained in the alkyl group and the phenyl group is a hydroxy group Which may be substituted.

[2] The curable resin composition according to the above [1], wherein the content of (D) is 1 part by mass or more and 25 parts by mass or less based on 100 parts by mass of (A).

[3] A coating film formed by the curable resin composition according to [1] or [2] above.

[4] A display device comprising the coating film according to [3] above.

According to the curable resin composition of the present invention, it is possible to form a coating film and a pattern excellent in heat resistance with less discoloration due to heat treatment.

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention is a curable resin composition comprising an addition polymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a structural unit derived from an unsaturated compound having an oxiranyl group (Hereinafter sometimes referred to as " polymer (A) ").

As the polymer (A), for example,

Polymer (A1): at least one (a) (hereinafter may be referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and an unsaturated compound having an oxiranyl group (a), (b), and (b), which are copolymerizable with the polymer (A2): (a) ) (Here, (a) and (b) are different monomers) (hereinafter sometimes referred to as "(c)").

(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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- Cyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] ] Esters;

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

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization-reactive surface and alkali solubility.

In the present specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

In the present invention, the unsaturated compound (b) having an oxiranyl group means a monomer having an oxirane ring and an unsaturated bond. (b1) (hereinafter may be referred to as " (b1) ") having an ethylenically unsaturated bond and a structure in which a chain-like aliphatic unsaturated hydrocarbon is epoxidized, and alicyclic unsaturated hydrocarbons, (B2) having an ethylenically unsaturated bond (hereinafter sometimes referred to as " (b2) ").

In the present invention, (b) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond, more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group. It is preferable that (b) is (b2).

(meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-methylglycidyl (meth) acrylate, Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl ether,? -Methyl- methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- 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, And compounds described in JP-A 7-248625.

(b2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl acrylate (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cychroma M100; manufactured by Daicel Chemical Industries, Ltd.) A compound represented by the formula (I) and a compound represented by the formula (II).

(2)

In the formulas (I) and (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group do.

X ¹ and X ² independently represent a single bond, -R ³ -, -R ³ -O-, -R ³ -S- or -R ³ -NH-.

R ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O

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

Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, Hydroxyethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

As R ¹ and R ² , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- And a 1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents the number of bonds with O) group, * -CH ₂ CH ₂ -O- group More preferably a single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). Preferably, the compound of the formula (I-1), the compound of the formula (I-3), the compound of the formula (I-5), the compound of the formula (I- ). (I-1), (I-7), (I-9) and (I-15).

(3)

[Chemical Formula 4]

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula ). (II-1), (II-7), (II-9) and (II-15).

[Chemical Formula 5]

[Chemical Formula 6]

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the ratio [formula (I): formula (II)] (molar ratio) is arbitrary, but preferably 5:95 to 95: , More preferably from 10:90 to 90:10, and particularly preferably from 20:80 to 80:20.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (Meth) acrylic acid alkyl esters;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, dicyclopentanil (Meth) acrylate), (meth) acrylic acid cycloalkyl esters such as 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;

(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- hydroxyethyl) bicyclo [2.2.1] 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cicarbonyl bicycles 2,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl ) Bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

Styrenes such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Acrylonitriles such as acrylonitrile and methacrylonitrile; Vinyl compounds such as vinyl chloride, vinylidene chloride, and vinyl acetate; Acrylamides such as acrylamide and methacrylamide; Diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

Methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3- Acryloyloxyethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl- Cetane, and 3-ethyl-3-acryloyloxyethyloxetane; oxetanyl group-containing (meth) acrylate esters;

(Meth) acrylate esters containing tetrahydrofuryl groups such as tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate; .

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and alkali solubility.

In the polymer [A1], the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of the structural units constituting the polymer [A1].

a structural unit derived from (a); 5 to 60% by mole (more preferably 10 to 50% by mole)

(b); 40 to 95 mol% (more preferably 50 to 90 mol%)

When the proportion of the structural unit of the polymer [A1] is in the above range, there is a tendency that the storage stability, the chemical resistance of the obtained coating film, the heat resistance and the mechanical strength are excellent.

The polymer [A1] can be produced by, for example, the method described in the "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) Can be prepared by reference to the literature.

Specifically, there is exemplified a method in which a prescribed amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by nitrogen, followed by stirring, heating, and keeping in a deoxidizing atmosphere. The polymerization initiator and solvent used herein are not particularly limited, and any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide Etc.). The solvent may be any one that dissolves the respective monomers. As the solvent (E) of the curable resin composition of the present invention, a solvent described later or the like may be used.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used. In particular, by using the same solvent as the solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is for preparing the curable resin composition, and the manufacturing process of the curable resin composition can be simplified.

In the polymer [A2], the proportion of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of the total structural units constituting the polymer [A2].

a structural unit derived from (a); 2 to 40 mol% (more preferably 5 to 35 mol%)

(b); 2 to 95 mol% (more preferably 5 to 80 mol%),

(c); 1 to 65% by mole (more preferably 1 to 60% by mole)

The total amount of the structural unit derived from (a) and the structural unit derived from (b) is preferably from 70 to 99 mol%, more preferably from 90 to 99 mol% based on the total moles of all structural units constituting the polymer [A2] And more preferably 99 mol%.

When the ratio of the structural unit of the polymer [A2] is within the above range, there is a tendency that the storage stability, the chemical resistance of the obtained coating film, the heat resistance and the mechanical strength are excellent.

The polymer [A2] can be produced by the same method as the polymer [A1].

Specific examples of the polymer [A1] include a copolymer of (meth) acrylic acid / formula (I-1), a copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / formula (I-4), a copolymer of (meth) acrylic acid / formula (I-5), a copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (I-7), copolymer of (meth) acrylic acid / formula (I-8), copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / formula (I-11), a copolymer of (meth) acrylic acid / formula (I-12), a copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / formula (I-14), a copolymer of (meth) acrylic acid / formula (I-15), a copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / formula (II-2), a copolymer of (meth) acrylic acid / formula (II-3) A copolymer of (meth) acrylic acid / formula (II-5), a copolymer of (meth) acrylic acid / formula (II-6) (Meth) acrylic acid / formula (II-8), a copolymer of (meth) acrylic acid / formula (II-9), a copolymer of (meth) acrylic acid / -11), a copolymer of (meth) acrylic acid / formula (II-12), a copolymer of (meth) acrylic acid / (Meth) acrylic acid / a copolymer of the formula (II-15), a copolymer of the (meth) acrylic acid / the formula (I-1) / the formula (II- (Meth) acrylic acid / formula (I-4) / formula (II-3) / copolymer of formula (II- (Meth) acrylic acid / copolymer of formula (I-6) / (II-6), (meth) acrylic acid / copolymer of formula (I- Methacrylic acid / formula (I-7) / formula (II-7) (Meth) acrylic acid / copolymer of the formula (I-8) / the formula (II-8), a copolymer of the (meth) acrylic acid / (Meth) acrylic acid / a copolymer of the formula (I-11) / the formula (II-11), a copolymer of the (meth) acrylic acid / formula (I- A copolymer of (meth) acrylic acid / formula (I-13) / formula (II-13), a copolymer of (meth) acrylic acid / formula (I- Copolymer of (meth) acrylic acid / formula (I-15) / formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (I-7) (I), a copolymer of (meth) acrylic acid / formula (I-1) / formula (II-7), a copolymer of crotonic acid / The copolymer of crotonic acid / formula (I-3), the copolymer of crotonic acid / formula (I-4), the copolymer of crotonic acid / Copolymer of the crotonic acid / the formula (I-8), the copolymer of the crotonic acid / the formula (I-7) Copolymers of crotonic acid / formula (I-10), copolymers of crotonic acid / formula (I-11), copolymers of crotonic acid / Copolymers of crotonic acid / formula (I-13), copolymers of crotonic acid / formula (I-14), copolymers of crotonic acid / (II-2), copolymers of crotonic acid / formula (II-3), copolymers of crotonic acid / formula (II-4), copolymers of crotonic acid / Copolymers of crotonic acid / formula (II-5), copolymers of crotonic acid / formula (II-6), copolymers of crotonic acid / Copolymers of crotonic acid / formula (II-10), copolymers of crotonic acid / formula (II-11), copolymers of crotonic acid / (II-13), copolymers of crotonic acid / formula (II-14), copolymers of crotonic acid / formula (II-15), copolymers of maleic acid / , A copolymer of maleic acid / formula (I-2), a copolymer of maleic acid / formula (I-3), a copolymer of maleic acid / Copolymers of maleic acid / formula (I-6), copolymers of maleic acid / formula (I-7), copolymers of maleic acid / ), A copolymer of maleic acid / formula (I-10), a copolymer of maleic acid / formula (I-11), a copolymer of maleic acid / -13), a copolymer of maleic acid / formula (I-14), a copolymer of maleic acid / formula (I-15), a copolymer of maleic acid / (II-2), a copolymer of maleic acid / formula (II-3), a copolymer of maleic acid / formula (II-4), a copolymer of maleic acid / / Copolymer of formula (II-6), a copolymer of maleic acid / formula (II-7), a copolymer of maleic acid / Maleic acid / copolymer of the formula (II-10), maleic acid / copolymer of the formula (II-11) (II-15), a copolymer of maleic acid / formula (II-14), a copolymer of maleic acid / formula (II-12) (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-1), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-5), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-6), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- Acid anhydride / copolymer of formula (I-11), (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-14), (meth) acrylic acid / maleic anhydride / copolymer of formula (I- (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- (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-7), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-8), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- 10), copolymers of (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-13), (meth) acrylic acid / maleic anhydride / copolymer of formula (II- Acrylic acid / maleic anhydride / copolymer of formula (II-14), and (meth) acrylic acid / maleic anhydride / copolymer of formula (II-15).

Specific examples of the polymer [A2] include copolymers of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / formula (I- Copolymers of (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (I-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / Copolymer of (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-9) / methyl Copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate (Meth) acrylic acid / formula (I-12) / methyl (meth) acrylate, A copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, A copolymer of (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate, (Meth) acrylic acid / formula (II-2) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / (Meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / Copolymers of (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate, copolymers of (meth) acrylic acid / formula (II-8) / methyl (meth) ) Acrylic acid / formula (II-9) / methyl (meth) (Meth) acrylic acid / copolymer of formula (II-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / A copolymer of (meth) acrylic acid / formula (II-12) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-13) / methyl (meth) (Meth) acrylic acid / a copolymer of the formula (II-15) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / (Meth) acrylic acid / a copolymer of the formula (II-1) / dicyclopentanyl (meth) acrylate, a copolymer of (meth) acrylic acid / (I-1) / dicyclopentanyl (meth) acrylate, copolymers of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, maleic acid / Cyclopentanyl (meth) acrylate Copolymers of (meth) acrylic acid / maleic anhydride / (I-1) / dicyclopentanyl (meth) acrylate, copolymers of (meth) acrylic acid / formula (I-1) / methyl (meth) Copolymers of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, copolymers of maleic acid / formula (II-1) / dicyclopentanyl (meth) (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / (Meth) acrylate / dicyclopentanyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate, (Meth) acrylate, copolymers of (meth) acrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / Phenyl (meth) (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / phenyl (meth) acrylate, copolymers of maleic acid / A copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, a copolymer of crotonic acid / formula (II-1) / phenyl (meth) (Meth) acrylate / maleic anhydride / copolymer of formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / A copolymer of diethyl maleate, a copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / formula (I- A copolymer of maleic acid / diethyl maleate, a copolymer of maleic acid / formula (I-1) / maleic acid (Meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / maleic acid anhydride / copolymer of diethyl maleate, copolymer of (meth) acrylic acid / maleic anhydride / (II-1) / copolymer of maleic acid / (II-1) / maleic acid, copolymer of (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / formula (I-1) / (meth) acrylate / diethyl maleate, copolymer of (meth) acrylic acid / (Meth) acrylic acid / copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / / Copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, crotonic acid / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / (I-1) / 2-hydroxyethyl (meth) acrylate Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / Copolymers of crotonic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, copolymers of maleic acid / formula (II-1) ) / 2-hydroxyethyl (meth) acrylate, copolymers of (meth) acrylic acid / maleic anhydride / formula (II-1) / 2-hydroxyethyl (meth) (Meth) acrylic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene / 2-ene, a copolymer of (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hepto-2-ene, a copolymer of (meth) acrylic acid / -1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / copolymer of formula (I-1) (Meth) acrylic acid / maleic anhydride / maleic anhydride / copolymers of maleic acid / formula (I-1) / bicyclo [2.2.1] hept- (Meth) acrylic acid / a copolymer of the formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hepto-2- (II-1) / bicyclo [2.2.1] hept-2-ene, copolymers of crotonic acid / ] Hept-2-ene, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / bicyclo [2.2.1] hept- Copolymers of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, copolymers of (meth) acrylic acid / Methacrylic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, Crotonic acid / formula (I-1) / N-cyclohexyl maleate Copolymer of maleic acid / formula (I-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexylmaleimide , Copolymers of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymers of crotonic acid / formula (II-1) / N-cyclohexylmaleimide, (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / N-cyclohexylmaleimide, a copolymer of (meth) acrylic acid / maleic acid / (Meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / -1) / styrene, copolymers of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymers of crotonic acid / formula (I- / Copolymer of formula (I-1) / styrene, (meth) acrylic acid / (Meth) acrylate / copolymer of formula (I-1) / methyl (meth) acrylate / styrene, crotonic acid / formula (II-1) / styrene (II-1) / styrene copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / styrene, (meth) acrylic acid / (Meth) acrylate / styrene copolymer, (meth) acrylic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / Copolymers of N-cyclohexylmaleimide / styrene, copolymers of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, crotonic acid / 1) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / maleic anhydride / 1) / N-cyclohexylmaleimide / styrene copolymer, ) Copolymer of acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene, crotonic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene , Copolymers of maleic acid / (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene , Copolymers of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene.

The weight average molecular weight of the polymer (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 25,000, and particularly preferably 5,000 to 15,000. When the weight average molecular weight of the polymer (A) is within the above range, the coating property tends to become good.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the obtained coating film tends to have excellent chemical resistance.

The acid value of the polymer (A) is preferably 30 mg-KOH / g to 180 mg-KOH / g, more preferably 40 mg-KOH / g to 150 mg-KOH / g, And more preferably not less than 50 mg-KOH / g and not more than 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the polymer, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the polymer (A) is in the above range, the resulting coating film tends to have excellent adhesion with the substrate.

The content of the polymer (A) is preferably 30 to 90 mass%, and more preferably 40 to 80 mass% with respect to the total of the content of the polymer (A) and the content of the (meth) acrylic compound (B). When the content of the polymer (A) is within the above range, the resulting coating film tends to have good adhesion with the substrate and good chemical resistance.

The curable resin composition of the present invention is a compound (B) having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter sometimes referred to as a "(meth) acryloyl group" (Hereinafter sometimes referred to as "(meth) acrylic compound (B)").

Examples of the (meth) acrylic compound (B) having one (meth) acryloyl group include the same ones as the compounds exemplified as (a), (b) and (c) Is preferred.

Examples of the (meth) acryl compound (B) having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3- butanediol (meth) acrylate, (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di Neopentyl glycol di (meth) acrylate, and 3-methylpentanediol di (meth) acrylate.

Examples of the (meth) acrylic compound (B) having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) iso (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride Water, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone- Caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate , Caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol (Meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, caprolactone-modified dipentaerythritol penta ) Acrylate and an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritol (meth) acrylate and an acid anhydride.

As the (meth) acrylic compound (B), a (meth) acrylic compound (B) having three or more (meth) acryloyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the (meth) acrylic compound (B) is preferably 10 to 233 parts by mass, more preferably 25 to 150 parts by mass based on 100 parts by mass of the polymer (A). When the content of the (meth) acrylic compound (B) is within the above range, the smoothness, reliability and mechanical strength of the obtained coating film tends to be good.

The curable resin composition of the present invention preferably contains a polymerization initiator (C). The polymerization initiator (C) is not particularly limited as long as it is a compound capable of initiating polymerization of the (meth) acrylic compound (B) by the action of light or heat, and known polymerization initiators can be used.

Examples of the polymerization initiator (C) include alkylphenone compounds, imidazole compounds, triazine compounds, acylphosphine oxide compounds and oxime compounds. Among them, a polymerization initiator containing at least one member selected from the group consisting of a non-imidazole compound, an alkylphenone compound and an oxime compound is preferable, and in particular, at least one member selected from the group consisting of an oxime compound and a non- Is more preferably a polymerization initiator. These polymerization initiators are preferable because they tend to be particularly sensitive.

The alkylphenone compound is a compound having as a partial structure? -Hydroxyalkylphenone,? -Alkoxyalkylphenone or? - (N-substituted amino) alkylphenone, specifically, diethoxyacetophenone, 2-hydroxy- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2- hydroxyethoxy) Hydroxy-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 < RTI ID = 0.0 & 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methylbenzyl) Butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Polynophenyl) butanone, 2- (2- 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 (2-butylbenzyl) 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- Amino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1 - (4-morpholinophenyl) butanone, an oligomer of 2-hydroxy-2-methyl-1- [4- - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one.

Examples of the oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy- Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan- 1-one-2-imine, N-acetoxy- 1- [ 3-yl] ethan-1-imine, N-acetoxy-1- [ Oxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- ) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372, JP-A 6-75373, etc.), 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxy) Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, Imidazole compounds in which the phenyl group in the 4'5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A 7-10913). Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the polymerization initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (C1) described later.

Also, a polymerization initiator having a group capable of chain transfer described in Japanese Patent Publication No. 2002-544205 may be used.

In the curable resin composition of the present invention, the polymerization initiator (C1) may be used together with the above-mentioned polymerization initiator (C). The polymerization initiator (C1) is used in combination with the polymerization initiator (C), and is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated by polymerization initiator. Examples of the polymerization initiator (C1) include a thioxanthone compound, a thiazoline compound, an alkoxyanthracene compound, an amine compound, and a carboxylic acid compound. By combining these with the polymerization initiator (C), a pattern can be obtained with high sensitivity.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- City Oak Mountain, and the like.

Examples of the thiazoline compound include the compounds represented by the formulas (III-1) to (III-3) and the compounds described in JP-A-2008-65319.

(7)

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and compounds described in JP-A-2009-139932.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- ) Benzophenone. ≪ / RTI >

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the polymerization initiator (C) is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 20 parts by mass, and still more preferably from 1 to 20 parts by mass, relative to 100 parts by mass in total of the polymer (A) and the (meth) And preferably 2 to 10 parts by mass. When the content of the polymerization initiator (C) is within the above range, a pattern tends to be obtained with high sensitivity, which is preferable.

The amount of the polymerization initiator (C1) to be used is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass based on 100 parts by mass of the total of the resin (A) and the (meth) acrylic compound (B) . When the amount of the polymerization initiator (C1) is in the above range, a pattern can be obtained with a high sensitivity, and the resulting pattern is preferable because of its good shape.

The curable resin composition of the present invention comprises an imidazole compound represented by the following formula (1) (hereinafter sometimes referred to as "imidazole compound (D)").

[Chemical Formula 8]

[In the formula (1), R ¹ represents a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms.

R ² to R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the hydrogen atom contained in the alkyl group and the phenyl group is a hydroxy group Which may be substituted]

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, And an undecyl group. The number of carbon atoms is preferably from 1 to 15, and more preferably from 1 to 12.

Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

 Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristoyl group, .

R ² is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the alkyl group and the hydrogen atom contained in the phenyl group may be substituted with a hydroxy group, more preferably a hydrogen atom, An alkyl group having 1 to 20 carbon atoms or a phenyl group, particularly preferably an alkyl or phenyl group having 1 to 20 carbon atoms.

R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the hydrogen atom contained in the alkyl group and the phenyl group may be substituted with a hydroxy group, more preferably a hydrogen atom , An alkyl group having 1 to 20 carbon atoms or a phenyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the imidazole compound (D) include 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 1-cyanomethyl- Methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole and the like. Among them, 1-benzyl-4-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable. These may be used alone or in combination of two or more.

The content of the imidazole compound (D) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 1.5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polymer (A). When the content of the imidazole compound (D) is in the above range, the obtained pattern or coating film tends to have excellent transparency.

The curable resin composition of the present invention preferably contains a thiol compound (T). The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule. Among them, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to carbon atoms of an aliphatic hydrocarbon structure is more preferable. When the thiol compound (T) is contained in the curable resin composition of the present invention, the sensitivity tends to increase.

Examples of the thiol compound (T) include hexane dithiol, decane dithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), butanediol bis ), Trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate) (Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris Pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane, and the like.

The content of the thiol compound (T) is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass, per 100 parts by mass of the polymerization initiator (C). When the content of the thiol compound (T) is within this range, sensitivity tends to be high and developability tends to be good.

The curable resin composition of the present invention preferably contains a solvent (E).

The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethylsulfoxide, and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 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, A brush, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclopentanone, cyclohexanone, isophorone, and the like.

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, and mesitylene.

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

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

An organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm on the coating property and drying surface of the solvent is preferable. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and mixed solvents containing them are preferable.

The content of the solvent (E) in the curable resin composition is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass, based on the curable resin composition. In other words, the solid content of the curable resin composition is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. Here, the solid content refers to the amount obtained by removing the solvent (E) from the curable resin composition. When the content of the solvent (E) is in the above range, the flatness of the film coated with the curable resin composition tends to be high.

The curable resin composition of the present invention preferably contains an antioxidant (F). Examples of the antioxidant (F) include 2-tert-butyl-6- (3- tert -butyl-2-hydroxy- Butylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert- butyl-4-hydroxy- ) Propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylene Bis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropane Pyranate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) A ", a" - (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3 Butylphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, etc. IRGANOX (registered trademark) 3114 ( BASF Japan Co., Ltd.) may be used.

The content of the antioxidant (F) is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the polymer (A). When the content of the antioxidant (F) is within the above range, the obtained coating film tends to have excellent heat resistance and pencil hardness. If the content of the antioxidant (F) exceeds 5 parts by mass, the pencil hardness may be lowered.

The curable resin composition of the present invention may contain a surfactant (G). Examples of the surfactant include a silicon surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

As the silicone surfactant, a surfactant having a siloxane bond can be mentioned. Concretely, it is preferable to use a silicone resin such as Tororensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether-denatured silicone oil SH8400 (trade name: Toor Dow Corning Co., , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Co., And the like.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, it is possible to use FUJINAT (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F552, (Registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Corporation (registered trademark)), F555, F555, F556, (Trade name) manufactured by Daikin Fine Chemical Research Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation). And preferably Megapack (registered trademark) F475.

The surfactant (G) is contained in the curable resin composition in an amount of 0.001 mass% to 0.2 mass%, preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.01 mass% or more and 0.05 mass% or less. By including the surfactant in this range, the flatness of the coating film can be improved.

The curable resin composition of the present invention may contain additives such as fillers, other polymer compounds, heat radical generators, ultraviolet absorbers, chain transfer agents, and adhesion promoters, if necessary.

Examples of the filler include glass, silica and alumina.

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

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

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

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

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, (Aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, Sisilran, and 3-aminopropyl the silane, N- phenyl-3-aminopropyltrimethoxysilane, N- phenyl-3-amino propyl silane in the tree.

In addition, the curable resin composition of the present invention contains substantially no coloring agent such as pigment and dye. That is, in the curable resin composition of the present invention, the content of the coloring agent in the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

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

When the curable resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. The average transmittance was measured using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm for a coating film having a thickness of 3 占 퐉 after heat curing (for example, 100 to 250 占 폚 for 5 minutes to 3 hours) . This makes it possible to provide a coating film excellent in transparency in the visible light region.

The curable resin composition of the present invention can be prepared by a known method such as polymer (A), (meth) acrylic compound (B), polymerization initiator (C) and imidazole compound (D) Followed by stirring and mixing. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 mu m.

The curable resin composition of the present invention can be formed as a coating film by applying it on a substrate such as a glass, metal, plastic substrate, a color filter, various insulating or conductive films, a driving circuit, or the like. It is preferable that the coating film is dried and cured. The obtained coating film may be patterned into a desired shape and used as a pattern. These coating films or patterns may be formed and used as a part of constituent parts such as a display device.

First, the curable resin composition of the present invention is applied onto a substrate.

As described above, the application can be carried out by using various applicators such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.

Next, it is preferable to remove the volatile components such as a solvent by drying or pre-baking. Thus, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not particularly limited and can be suitably adjusted according to the material to be used and the application, and is, for example, about 1 to 6 mu m.

The obtained uncured coating film is irradiated with light, for example, a mercury lamp, ultraviolet rays generated from the light emitting diode, or the like through a mask for forming a desired pattern. The shape of the mask at this time is not particularly limited, and various shapes can be mentioned. The transmittance of the mask light-transmitting portion is not particularly limited as long as it transmits light from the light source. The width, height, and the like of the pattern can be appropriately adjusted in accordance with the mask size, the transmittance of the mask transparent portion, and the like.

In recent exposures, light having a wavelength of less than 350 nm is cut using a filter that cuts this wavelength, or light having wavelengths around 436 nm, around 408 nm, and around 365 nm is taken out by a bandpass filter So that the parallel rays can be uniformly irradiated onto the entire exposure surface. In order to precisely align the mask and the substrate at this time, an apparatus such as a mask aligner or a stepper may be used.

Thereafter, a desired pattern shape can be obtained by bringing the coating film into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, an unexposed portion.

The developing method may be any of a liquid mounting method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development.

The developing solution used for development is preferably an aqueous solution of an alkaline compound.

The alkaline compound may be any of inorganic and organic alkaline compounds.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, sodium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.

The organic alkaline compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

The concentration of these inorganic and organic alkaline compounds in the aqueous solution is preferably 0.01 to 10 mass%, and more preferably 0.03 to 5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

The concentration of the surfactant in the alkali developing solution is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

After the development, washing with water may be carried out, and further post baking may be carried out if necessary. The post bake is preferably carried out at a temperature in the range of 150 to 240 캜 for 10 to 180 minutes, for example.

The coating film or pattern thus obtained is useful as, for example, a photo-spacer used in a liquid crystal display device, and an overcoat that can be patterned. In the patterning exposure of the uncured coating film, holes can be formed by using a photomask for forming a hole, which is useful as an interlayer insulating film. Further, at the time of exposure for the uncured coating film, the transparent film can be formed by performing only the front exposure and the heating curing or the heating curing only without using the photomask. This transparent film is useful as an overcoat. It can also be used for a display device such as a touch panel. Thus, a display device having a high-quality coating film or pattern can be manufactured at a high yield.

The curable resin composition of the present invention can be suitably used as a material for forming various films and patterns such as a transparent film, a pattern, a photo spacer, an overcoat, an insulating film, a projection for controlling liquid crystal orientation, A micro lens, a coat layer, and the like. In addition, a color filter, an array substrate, and the like having these coating films or patterns as a part of their constituent parts, and display devices including these color filters and / or array substrates, for example, liquid crystal display devices, organic EL devices, Electronic papers and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part " are by mass% and mass part, respectively, unless otherwise specified.

(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 make a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 DEG C with stirring. 40 parts of methacrylic acid; 360 parts of a mixture of monomer (I-1) and monomer (II-1) (monomer (I-1): monomer (II-1) in the mixture = 50: 50) was dissolved in 190 parts of diethylene glycol ethyl methyl ether Was prepared. This solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel.

[Chemical Formula 9]

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was dropped into a flask over 5 hours using another dropping pump Respectively. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 캜 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 8000, a molecular weight distribution (Mw / Mn) of 1.91 and an acid value of 60 mg-KOH / g (acid value in terms of solid content).

(Synthesis Example 2)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added, And heated to 70 deg. Subsequently, a mixture of 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02.6] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) : 50) was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was dropped into a flask over 4 hours using another dropping funnel Respectively. After the dropping of the polymerization initiator solution was completed, the solution was kept at 70 캜 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% and an acid value of 110 mg-KOH / g ≪ / RTI > The obtained resin Ab had a weight average molecular weight (Mw) of 13,400 and a molecular weight distribution (Mw / Mn) of 2.50.

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

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

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Tosoh)

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

(Examples 1 to 8 and Comparative Example 1)

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

Unless otherwise specified in Table 1, the unit is " part ". The number of parts contained in the polymer (A) represents a part by mass in terms of solid content.

Polymer (A); Aa; The resin Aa obtained in Synthesis Example

Polymer (A); Ab; The resin Ab obtained in Synthesis Example

(Meth) acrylic compound (B); Ba; Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

A polymerization initiator (C); Ca; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,

A polymerization initiator (C); Cb; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co.,

Polymerization initiator (C1); C1a; 2- (2-naphthoylmethylene) -3-methylbenzothiazoline

Imidazole compound (D); Da; 1-benzyl-2-phenylimidazole (Cure Sol 1B2PZ; manufactured by Shikoku Chemical Industry Co., Ltd.)

[Chemical formula 10]

Imidazole compound (D); Db; 1- (2-cyanoethyl) -2-undecylimidazole (Curezol C11Z-CN; manufactured by Shikoku Chemical Industry Co., Ltd.)

(11)

Imidazole compound (D); Dc; Methyl-2-ethyl-4-methylimidazole (Curezol 2E4MZ-CN; manufactured by Shikoku Chemical Industry Co., Ltd.)

[Chemical Formula 12]

Thiol compound (T); Ta; Pentaerythritol tetrakispropionate (PEMP; SC Organic Chemicals Co., Ltd.)

Antioxidant (F); Fa; 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) IRGANOX (registered trademark) 3114, manufactured by BASF Japan Co., Ltd.)

Solvent (E); Ea; Propylene glycol monomethyl ether acetate

Solvent (E); Eb; 3-Methoxy-1-butanol

Solvent (E); Ec; Diethylene glycol ethyl methyl ether

Solvent (E); Ed; 3-ethoxyethyl propionate

Solvent (E); Ee; 3-methoxybutylacetate

The solvent (E) is mixed so that the solid content of the curable resin composition is the " solid content (%) " in Table 1, and the values of the solvent components (Ea) to (Ee) in the solvent (E) .

<Viscosity Measurement>

The viscosity of the obtained curable resin composition was measured using a viscometer (model: TV-30; manufactured by Toray Industries, Ltd.). The results are shown in Table 2.

&Lt; Transmittance of curable resin composition &gt;

Using the ultraviolet visible near infrared spectrophotometer (V-650; manufactured by Nihon Spectroscopy, Ltd.) (quartz cell, optical path length: 1 cm), the curable resin composition obtained had an average transmittance at 400 to 700 nm %) Was measured. The results are shown in Table 2.

<Fabrication of Coating Film>

A 2-inch square glass substrate (Eagle XG; Corning) was washed sequentially with a neutral detergent, water and 2-propanol, and then dried. The curable resin composition was spin-coated on the glass substrate so that the film thickness after post-baking was 3.0 占 퐉, and then pre-baked in a hot plate at 90 占 폚 for 2 minutes. Subsequently, an exposure machine (TME-150 RSK; The coating film after pre-baking was exposed to light at an exposure amount of 100 mJ / cm &lt; 2 &gt; (based on 365 nm) in an atmospheric atmosphere. In this exposure, the radiation from the ultra-high pressure mercury lamp was irradiated through an optical filter (UV-33; manufactured by Asahi Techno Glass Co., Ltd.). After exposure, the film was heated at 230 占 폚 for 20 minutes to obtain a coated film.

&Lt; Transmittance of coating film &

The average film transmittance (%) at 400 to 700 nm was measured for a coating film obtained using a microscopic spectroscopic photometry apparatus (OSP-SP200, manufactured by OLYMPUS CO., LTD.). The results are shown in Table 2.

<Heat resistance>

The obtained coating film was heated in an oven at 240 占 폚 for 60 minutes to measure the film thickness and the transmittance before and after heating, and the film thickness change (%) and the transmittance change (%) were determined according to the following formula. The film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The closer to 100%, the smaller the change before and after heating, and the better the heat resistance. When the heat resistance of the coating film is high, the pattern formed by the same curable resin composition also has high heat resistance. The results are shown in Table 2.

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

Film thickness change (%); (Film thickness after heating (占 퐉) / Film thickness before heating (占 퐉)) 占 100

&Lt; Pattern formation &gt;

A 2-inch square glass substrate (Eagle 2000; Corning) was washed sequentially with a neutral detergent, water and 2-propanol, and then dried. On this glass substrate, the curable resin composition was applied by spin-coating so that the post-baked pattern had a thickness of 3 占 퐉. Subsequently, the reduced pressure was reduced to 0.5 torr with a vacuum dryer (VCD Microtech Co., Ltd.) and dried to form a coating film. This coated film was pre-baked in a hot plate at 90 캜 for 2 minutes. (Based on 365 nm) of 100 mJ / cm &lt; 2 &gt; in an air atmosphere using an exposure apparatus (TME-150RSK; manufactured by Topcon Co., To expose a coating film after pre-baking. In this exposure, the radiation from the ultra-high pressure mercury lamp was irradiated through an optical filter (UV-33; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask having a diameter of 5 탆, 6 탆, 7 탆, 8 탆, 9 탆, 10 탆, 11 탆, 12 탆, 13 탆, 14 탆, 15 탆, 16 탆, 17 탆, 18 탆, 19 Mu m, and 20 mu m, and a pattern in which the interval between the circularly projected portions was 100 mu m was formed on the same plane was used.

After exposure, the substrate was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 DEG C for 60 seconds to develop and rinse. Then, post-baking was performed in an oven at 230 DEG C for 20 minutes to obtain a pattern .

<Evaluation of resolution>

The pattern obtained by a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) was observed, and the minimum line width at which the pattern was separated was taken as the resolution. The results are shown in Table 2.

From the above results, it was confirmed that the coating film obtained by the curable resin composition of the present invention had a small change in transmittance in the heat resistance test and little coloring by heat treatment.

According to the curable resin composition of the present invention, it is possible to form a coating film and a pattern excellent in heat resistance.

Claims (4)

A curable resin composition comprising (A), (B), (C) and (D)
(A) at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a copolymer (b2) of a structure in which an alicyclic unsaturated hydrocarbon is epoxidized and an ethylenic unsaturated bond- , And / or
(A) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, (b) a monomer (b2) having an epoxidized alicyclic unsaturated hydrocarbon and an ethylenically unsaturated bond, and And a monomer (c) copolymerizable with (b2)
(B) a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group
(C) Polymerization initiator
(D) a compound represented by the formula (1)
[Chemical Formula 13]

[In the formula (1), R ¹ represents a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms,
R ² to R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the hydrogen atom contained in the alkyl group and the phenyl group is a hydroxy group Which may be substituted,
Wherein the compound represented by the formula (1) of the formula (D) is 1-benzyl-2- phenylimidazole, 1- (2-cyanoethyl) -2-undecylimidazole and 1- ) -2-ethyl-4-methylimidazole,
(D) is not less than 1 part by mass and not more than 25 parts by mass based on 100 parts by mass of (A)
(C) is a polymerization initiator containing at least one member selected from the group consisting of a nonimidazole compound, an alkylphenone compound and an oxime compound,
Curable resin composition. The method according to claim 1,
(D) is not less than 1.5 parts by mass and not more than 20 parts by mass based on 100 parts by mass of (A). A coating film formed by the curable resin composition according to claim 1 or 2. A display device comprising the coating film according to claim 3.