KR20120134024A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to form excellent coating film and patterns with excellent heat resistance and to have low coloring by heat treatment. CONSTITUTION: A curable resin composition comprises: an addition polymer which comprises a unit structure originated from an unsaturated compound with an oxyranyl group, and a unit structure originated from at least one kind selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; a polymerization initiator; and a compound indicated in chemical formula 1. In chemical formula 1, R^1 benzyl group or C2-5 cyanoalkyl group, each of R^2-R^4 is hydrogen, halogen, a C1-20 alkyl group, a phenyl group, a nitro group or a C1-20 acyl group.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition.

Coating films, such as a color filter protective film, are used for a liquid crystal display device etc. as a member. The color filter protective film is a coating film used for flattening the unevenness of the surface formed by the underlying color filter or black matrix, or for protecting the color filter and the like from the chemicals used for forming the upper layer member. . In order to form a color filter protective film, curable resin composition is used.

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

Japanese Unexamined Patent Publication No. 2010-152335

The coating film and pattern formed using the said curable resin composition conventionally known are not necessarily high enough in heat resistance, and may be easy to be colored by heat processing.

The present invention is the following [1]? [4] to provide.

[1] curable resin composition containing the following (A), (B), (C) and (D):

(A) An addition polymer containing the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the unsaturated compound which has an oxiranyl group.

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

(C) polymerization initiator

(D) Compound represented by Formula (1)

[Formula 1]

[In formula (1), R <^1> is a benzyl group or C2? 5 represents a cyanoalkyl group,

R ² ? R ⁴ independently of one another is a hydrogen atom, a halogen atom, carbon atoms? 20 alkyl, phenyl, nitro or C 1? 20 acyl group, and the hydrogen atom contained in this alkyl group and this phenyl group may be substituted by the hydroxy group].

[2] Curable resin composition as described in said [1] whose content of (D) is 1 mass part or more and 25 mass parts or less with respect to 100 mass parts of (A).

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

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

According to the curable resin composition of this invention, coloring by heat processing is few, and the coating film and pattern excellent in heat resistance can be formed.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Curable resin composition of this invention is an addition polymer containing the structural unit derived from the at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the unsaturated compound which has an oxiranyl group. (Hereinafter, it may be called "polymer (A).)."

As the polymer (A), for example

Polymer [A1]: at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter, may be referred to as "(a)") and an unsaturated compound having an oxiranyl group ( b) A copolymer formed by polymerizing (hereinafter sometimes referred to as "(b)"), a polymer [A2]: a monomer copolymerizable with (a) and (b) and (a) and (b) (c) ), But the copolymer etc. which superpose | polymerize (the following (a) and (b) are different monomers) (hereinafter may be called "(c)") are mentioned.

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

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

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

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

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

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

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

In this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Quot ;, &quot; (meth) acryloyl &quot;, and &quot; (meth) acrylate &quot;

In this invention, the unsaturated compound (b) which has an oxiranyl group means the monomer which has an unsaturated bond with an oxirane ring. As (b), the monomer (b1) (Hereinafter, it may be called "(b1)") which has the structure and ethylenically unsaturated bond which the chain aliphatic unsaturated hydrocarbon epoxidized, for example, and an alicyclic unsaturated hydrocarbon are epoxy The monomer (b2) (Hereinafter, it may be called "(b2)") which has a structured structure and ethylenically unsaturated bond is mentioned.

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

Specific examples of (b1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate and glycidyl vinyl ether. Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether , α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycid) Dyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, The compound described in Unexamined-Japanese-Patent No. 7-248625, etc. are mentioned.

Examples of (b2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, ceoxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethylacrylic Rate (for example, cycloma A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cycloma M100; manufactured by Daicel Chemical Industry Co., Ltd.), The compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula 2]

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

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

R ³ has 1? The alkanediyl group of 6 is shown.

* Represents the number of bonds with O

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

As a hydroxyalkyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1- Methyl ethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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

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

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

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

(3)

[Formula 4]

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

[Chemical Formula 5]

[Formula 6]

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively and may use 2 or more types together. When using the compound represented by Formula (I) and the compound represented by Formula (II) together, the ratio [Formula (I): Formula (II)] (molar ratio) is arbitrary, Preferably it is 5:95? 95: 5, more preferably 10: 90? 90: 10, particularly preferably 20: 80? 80: 20.

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

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

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

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

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

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

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

Styrene, such as styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxy styrene;

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;

3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3- Acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl ox Oxetanyl group-containing (meth) acrylic acid esters such as cetane and 3-ethyl-3-acryloyloxyethyl oxetane;

Tetrahydrofurfuryl group-containing (meth) acrylic acid esters such as tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate; Can be.

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

In polymer [A1], it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit which comprises polymer [A1].

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

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

When the ratio of the structural unit of polymer [A1] exists in the said range, it exists in the tendency which is excellent in storage stability, the chemical resistance, heat resistance, and mechanical strength of the coating film obtained.

The polymer [A1] is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Kogyo Co., Ltd. Chemical Co., Ltd., First Edition, First Printing, issued March 1, 1972), and the citations described in this document. It can be manufactured with reference to the literature.

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

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

In polymer [A2], it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total mole number of all the structural units which comprise polymer [A2].

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

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

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

Moreover, the sum total of the structural unit derived from (a) and the structural unit derived from (b) is 70? With respect to the total mole number of all the structural units which comprise polymer [A2]. 99 mol% is preferable and 90? 99 mol% is more preferable.

When the ratio of the structural unit of polymer [A2] exists in the said range, it exists in the tendency which is excellent in storage stability, the chemical-resistance, heat resistance, and mechanical strength of the coating film obtained.

Polymer [A2] can be manufactured by the same method as Polymer [A1].

As a specific example of polymer [A1], the copolymer of (meth) acrylic acid / formula (I-1), the copolymer of (meth) acrylic acid / formula (I-2), (meth) acrylic acid / formula (I-3) ), Copolymer of (meth) acrylic acid / formula (I-4), copolymer of (meth) acrylic acid / formula (I-5), copolymer of (meth) acrylic acid / formula (I-6), (Meth) acrylic acid / copolymer of formula (I-7), (meth) acrylic acid / copolymer of formula (I-8), (meth) acrylic acid / copolymer of formula (I-9), (meth) acrylic acid / Copolymer of formula (I-10), copolymer of (meth) acrylic acid / formula (I-11), copolymer of (meth) acrylic acid / formula (I-12), (meth) acrylic acid / formula (I-13 ), Copolymer of (meth) acrylic acid / formula (I-14), copolymer of (meth) acrylic acid / formula (I-15), copolymer of (meth) acrylic acid / formula (II-1), Copolymer of (meth) acrylic acid / formula (II-2), copolymer of (meth) acrylic acid / formula (II-3), and copolymer of (meth) acrylic acid / formula (II-4) Polymer, copolymer of (meth) acrylic acid / formula (II-5), copolymer of (meth) acrylic acid / formula (II-6), copolymer of (meth) acrylic acid / formula (II-7), (meth) Copolymer of acrylic acid / formula (II-8), copolymer of (meth) acrylic acid / formula (II-9), copolymer of (meth) acrylic acid / formula (II-10), (meth) acrylic acid / formula (II -11) copolymer, (meth) acrylic acid / copolymer of formula (II-12), (meth) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / air of formula (II-14) Copolymer, copolymer of (meth) acrylic acid / formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1), (meth) acrylic acid / formula (I-2) / Copolymer of formula (II-2), (meth) acrylic acid / formula (I-3) / copolymer of formula (II-3), (meth) acrylic acid / formula (I-4) / formula (II-4 Copolymer of (meth) acrylic acid / formula (II-5) / formula (II-5), copolymer of (meth) acrylic acid / formula (I-6) / formula (II-6) (Meth) acrylic acid / formula (I-7) / formula (II-7) Copolymer of (meth) acrylic acid / formula (I-8) / formula (II-8), copolymer of (meth) acrylic acid / formula (I-9) / formula (II-9), (meth ) Acrylic acid / copolymer of formula (I-10) / formula (II-10), (meth) acrylic acid / copolymer of formula (I-11) / formula (II-11), (meth) acrylic acid / formula (I -12) / copolymer of formula (II-12), (meth) acrylic acid / copolymer of formula (I-13) / formula (II-13), (meth) acrylic acid / formula (I-14) / formula ( Copolymer of (II-14), copolymer of (meth) acrylic acid / formula (I-15) / formula (II-15), and air of (meth) acrylic acid / formula (I-1) / formula (I-7) Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-7), copolymer of crotonic acid / formula (I-1), copolymer of crotonic acid / formula (I-2), Crotonic acid / copolymer of formula (I-3), crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5), air of crotonic acid / formula (I-6) Copolymer, copolymer of crotonic acid / formula (I-7), copolymerization of crotonic acid / formula (I-8) Sieve, copolymer of crotonic acid / formula (I-9), copolymer of crotonic acid / formula (I-10), copolymer of crotonic acid / formula (I-11), crotonic acid / formula (I-12) Copolymer of, crotonic acid / copolymer of formula (I-13), copolymer of crotonic acid / formula (I-14), copolymer of crotonic acid / formula (I-15), crotonic acid / formula (II- Copolymer of 1), copolymer of crotonic acid / formula (II-2), copolymer of crotonic acid / formula (II-3), copolymer of crotonic acid / formula (II-4), crotonic acid / formula ( II-5) copolymer, crotonic acid / copolymer of formula (II-6), crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / Copolymer of formula (II-9), copolymer of crotonic acid / formula (II-10), copolymer of crotonic acid / formula (II-11), copolymer of crotonic acid / formula (II-12), croton Copolymer of acid / formula (II-13), copolymer of crotonic acid / formula (II-14), copolymer of crotonic acid / formula (II-15), copolymerization of maleic acid / formula (I-1) , Copolymer of maleic acid / formula (I-2), copolymer of maleic acid / formula (I-3), copolymer of maleic acid / formula (I-4), maleic acid / formula (I-5) Copolymer, maleic acid / copolymer of formula (I-6), maleic acid / copolymer of formula (I-7), maleic acid / copolymer of formula (I-8), maleic acid / formula (I-9) ), Copolymer of maleic acid / formula (I-10), copolymer of maleic acid / formula (I-11), copolymer of maleic acid / formula (I-12), maleic acid / formula (I) -13) copolymer, maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15), maleic acid / copolymer of formula (II-1), maleic acid / formula Copolymer of (II-2), copolymer of maleic acid / formula (II-3), copolymer of maleic acid / formula (II-4), copolymer of maleic acid / formula (II-5), maleic acid / Copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / copolymer of formula (II-8), maleic acid / copolymer of formula (II-9), Maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11) Polymer, maleic acid / copolymer of formula (II-12), maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / formula (II-15) Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-2), (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-5), ( Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-6), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-7), (meth) acrylic acid / maleic anhydride / formula (I- 8) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-10), (meth) acrylic acid / male Acid anhydride / copolymer of formula (I-11), (meth) acrylic acid / maleic anhydride / Copolymer of (I-12), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-13), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-14), (meth) Copolymer of acrylic acid / maleic anhydride / formula (I-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1), (meth) acrylic acid / maleic anhydride / formula (II-2) Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-3), copolymer of (meth) acrylic acid / maleic anhydride / 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 formula (II-7), ( Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-8), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-9), (meth) acrylic acid / maleic anhydride / formula (II- 10) copolymer, (meth) acrylic acid / maleic anhydride / Copolymer of (II-11), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-12), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-13), (meth) The copolymer of acrylic acid / maleic anhydride / formula (II-14), the copolymer of (meth) acrylic acid / maleic anhydride / formula (II-15), etc. are mentioned.

As a specific example of polymer [A2], the copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth) acrylate Copolymer of, (meth) acrylic acid / copolymer of formula (I-3) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (I-5) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, (meth) acrylic acid / formula (I) -7) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-9) / methyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, and air of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (I-12) / methyl (meth) Copolymer of methacrylate, copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (II-2) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-3) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-4) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate Copolymer of (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate, (meth ) Acrylic acid / formula (II-9) / methyl (meth) Copolymer of methacrylate, copolymer of (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (II-12) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (II-14) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / Copolymer of dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula ( Copolymer of II-1) / dicyclopentanyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (I-1) / dish Clofentanil (meth) acrylic Copolymer of meth, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylic Copolymer of rate / dicyclopentanyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (II-1) / dicyclopentanyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl ( Copolymer of meth) acrylate / dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (II-1) Copolymer of / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / formula (I-1) / Phenyl (meth) ah Copolymer of malate, copolymer of maleic acid / formula (I-1) / phenyl (meth) acrylate, air of (meth) acrylic acid / maleic anhydride / formula (I-1) / phenyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / phenyl (meth) acrylate , Copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / diethyl maleate, (meth) acrylic acid / Copolymer of formula (II-1) / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / formula (I-1) / Copolymer of diethyl maleate, maleic acid / formula (I-1) / maleic acid Copolymer of diethyl, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / maleic acid Copolymer of ethyl, copolymer of crotonic acid / formula (II-1) / diethyl maleate, copolymer of maleic acid / formula (II-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / formula ( Copolymer of II-1) / diethyl maleate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / diethyl maleate, (meth) acrylic acid / formula (I-1) / Copolymer of 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1 ) / Copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, crotonic acid / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / Formula (I-1) / 2-hydroxyethyl (meth) acrylic Copolymer of meth, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth Copolymer of acrylate / 2-hydroxyethyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / formula Copolymer of (2) -hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / bicyclo [2.2.1] hepto- Copolymer of 2-ene, (meth) acrylic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hepto-2-ene, (meth) acrylic acid / formula (I-1) / formula (II -1) / copolymer of bicyclo [2.2.1] hepto-2-ene, crotonic acid / formula (I-1) / bicycle Copolymer of rho [2.2.1] hepto-2-ene, maleic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hepto-2-ene, (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-1) / bicyclo [2.2.1] hepto-2-ene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hepto Copolymer of 2-ene, crotonic acid / formula (II-1) / bicyclo [2.2.1] copolymer of hepto-2-ene, maleic acid / formula (II-1) / bicyclo [2.2.1 ] Copolymer of hepto-2-ene, (meth) acrylic acid / maleic anhydride / formula (II-1) / bicyclo [2.2.1] copolymer of hepto-2-ene, (meth) acrylic acid / formula (II -1) / methyl (meth) acrylate / bicyclo [2.2.1] hepto-2-ene copolymer, (meth) acrylic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide, ( Copolymer of (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, Crotonic Acid / Formula (I-1) / N-cyclohexylmale Copolymer of mid, 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, Copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth) acrylic acid Copolymer of / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / styrene, (meth) acrylic acid / formula (II -1) / copolymer of styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymer of crotonic acid / formula (I-1) / styrene, maleic acid / Copolymer of formula (I-1) / styrene, (meth) acrylic acid / horse Copolymer of leric anhydride / formula (I-1) / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / styrene, crotonic acid / formula (II-1) / styrene Copolymer of, copolymer of maleic acid / formula (II-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / styrene, (meth) acrylic acid / formula (II-1) Copolymer of () / methyl (meth) acrylate / styrene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / Copolymer of N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, crotonic acid / formula (I- 1) / N-cyclohexyl maleimide / styrene copolymer, maleic acid / formula (I-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (I- 1) / N-cyclohexylmaleimide / styrene copolymer, (meth A copolymer of acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexyl maleimide / styrene, copolymer of crotonic acid / formula (II-1) / N-cyclohexyl maleimide / styrene , Copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene And copolymers of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene.

The weight average molecular weight of polystyrene conversion of a polymer (A) becomes like this. Preferably it is 3,000? 100,000, more preferably 5,000? 50,000, more preferably 5,000? 25,000, particularly preferably 5,000? 15,000. If the weight average molecular weight of a polymer (A) exists in the said range, there exists a tendency for applicability | paintability to become favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer (A) becomes like this. 6.0, more preferably 1.2? 4.0. When molecular weight distribution exists in the said range, the coating film obtained tends to be excellent in chemical resistance.

The acid value of the polymer (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, particularly preferably 50 mg-KOH / g or more and 135 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of a polymer (A) exists in said range, the coating film obtained tends to be excellent in adhesiveness with a board | substrate.

As for content of a polymer (A), with respect to the sum total of content of a polymer (A) and content of a (meth) acryl compound (B), Preferably it is 30? 90 mass%, More preferably, it is 40? 80 mass%. When content of a polymer (A) exists in said range, the coating film obtained tends to become favorable adhesiveness and chemical-resistance with a board | substrate.

The curable resin composition of this invention has the compound (B) which has at least 1 sort (s) of groups chosen from the group which consists of acryloyl group and a methacryloyl group (Hereinafter, it may be called "(meth) acryloyl group.") It is preferable to contain (hereinafter, it may be called "(meth) acryl compound (B)").

As a (meth) acryl compound (B) which has one (meth) acryloyl group, the thing similar to the compound illustrated as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester Are preferred.

As a (meth) acryl compound (B) which has two (meth) acryloyl groups, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, and 1, 6- hexanediol di (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( Meth) acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, ethoxylated Neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Examples of the (meth) acryl compound (B) having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) iso. Cyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, Half of tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride Water, reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, reactant of tripentaerythritolhepta (meth) acrylate and acid anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified Pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipenta Erythritol penta (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 tripentaery Litholhepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and a reaction product of an acid anhydride, caprolactone modified dipentaerythritol penta (meth The reactant of an acrylate and an acid anhydride, the reactant of a caprolactone modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride, etc. are mentioned.

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

The content of the (meth) acryl compound (B) is preferably 10? To 100 parts by mass of the polymer (A). 233 parts by mass, more preferably 25? 150 parts by mass. When content of a (meth) acryl compound (B) exists in the said range, there exists a tendency for the smoothness, reliability, and mechanical strength of the coating film obtained to become favorable.

It is preferable that curable resin composition of this invention 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) acryl compound (B) by the action of light or heat, and a known polymerization initiator can be used.

As a polymerization initiator (C), an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound, an oxime compound is mentioned, for example. Especially, it is preferable that it is a polymerization initiator containing at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an alkylphenone compound, and an oxime compound, and at least 1 sort (s) especially chosen from the group which consists of an oxime compound and a biimidazole compound. It is more preferable that it is a polymerization initiator containing. If it is these polymerization initiators, since there exists a tendency to become especially high sensitivity, it is preferable.

The alkylphenone compound is a compound having α-hydroxyalkylphenone, α-alkoxyalkylphenone or α- (N-substituted amino) alkylphenone as a partial structure, specifically, diethoxyacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 2-hydride Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one, 1-hydroxycyclohexylphenylketone, 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2 -(2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-mor Polynophenyl) butanone, 2- (2- Propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -(2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morph Polynophenyl) butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromobenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-chlorobenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-bro Mobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methoxybenzyl) -2-dimeth Amino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- ( 2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1 Oligomer of-(4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (dimethylamino) -2 -[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one and the like.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-ethoxycarbonyloxy-1-phenylpropan-1-one-2- Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyl Oxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. You may use commercial items, such as Irgacure OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation).

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl ) -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'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Laid-Open Patent Publication No. 62-174204, etc.), 4, The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) etc. in which the phenyl group of a 4'5,5'-position is substituted by the carboalkoxy group. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ＇, 5,5'-tetraphenylbiimidazole and 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 and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide compound.

Furthermore, as a polymerization initiator (C), 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-phenanthrene quinone, 2-ethylanthraquinone and camphor quinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with the polymerization start adjuvant (C1) mentioned later.

Moreover, you may use the polymerization initiator which has group which can cause the chain transfer described in Unexamined-Japanese-Patent No. 2002-544205.

In curable resin composition of this invention, you may use a polymerization start adjuvant (C1) further with the polymerization initiator (C) mentioned above. A polymerization start adjuvant (C1) is used in combination with a polymerization initiator (C), and is a compound or sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. As a polymerization start adjuvant (C1), a thioxanthone compound, a thiazolin compound, an alkoxy anthracene compound, an amine compound, a carboxylic acid compound, etc. are mentioned. By combining these and a polymerization initiator (C), a pattern can be obtained with high sensitivity.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxide Citioxanthone etc. are mentioned.

As a thiazolin compound, it is a formula (III-1)? The compound represented by Formula (III-3), the compound of Unexamined-Japanese-Patent No. 2008-65319, etc. are mentioned.

[Formula 7]

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene, the compound of Unexamined-Japanese-Patent No. 2009-139932, etc. are mentioned.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4'-bis (diethylamino Aromatic amine compounds, such as) benzophenone, are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxy acetic acid.

The content of the polymerization initiator (C) is preferably 0.5? To 100 parts by mass in total of the polymer (A) and the (meth) acryl compound (B). 30 parts by mass, more preferably 1? 20 parts by mass, more preferably 2? 10 parts by mass. When content of a polymerization initiator (C) exists in said range, there exists a tendency which can obtain a pattern with high sensitivity, and it is preferable.

The usage-amount of a polymerization start adjuvant (C1) becomes like this. Preferably it is 0.1? 10 parts by mass, more preferably 0.3? 7 parts by mass. When the quantity of a polymerization start adjuvant (C1) exists in said range, since a pattern can be obtained with high sensitivity and the pattern obtained is favorable in shape, it is preferable.

Curable resin composition of this invention contains the imidazole compound represented by following formula (1) (Hereinafter, it may be called "imidazole compound (D).).

[Formula 8]

[In formula (1), R <^1> is a benzyl group or C2? The cyanoalkyl group of 5 is shown.

R ² ? R ⁴ independently of one another is a hydrogen atom, a halogen atom, carbon atoms? 20 alkyl, phenyl, nitro or C 1? 20 acyl group, and the hydrogen atom contained in the alkyl group and the phenyl group may be substituted with a hydroxy group]

Carbon number 1? Examples of the alkyl group of 20 include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, heptadecyl group, undecyl group and the like. These are mentioned, Preferably it is C1-C? 15, More preferably, it is C1-C? 12 is.

Carbon number 2? Examples of the cyanoalkyl group 5 include cyanomethyl group, cyanoethyl group, cyanopropyl group, cyanobutyl group, cyanopentyl group, and the like.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example.

 Carbon number 1? Examples of the 20 acyl group include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group and stearoyl group and the like. .

R ² is preferably independently of each other a hydrogen atom, carbon 1? It is an alkyl group or a phenyl group of 20, and the hydrogen atom contained in this alkyl group and this phenyl group may be substituted by the hydroxy group, More preferably, it is a hydrogen atom and C1-C? It is an alkyl group or a phenyl group of 20, Especially preferably, it is C1-C? It is an alkyl group or a phenyl group of 20.

R ³ and R ⁴ are preferably independently of each other a hydrogen atom, C 1? It is an alkyl group or a phenyl group of 20, and the hydrogen atom contained in this alkyl group and this phenyl group may be substituted by the hydroxy group, More preferably, it is a hydrogen atom and C1-C? It is an alkyl group or a phenyl group of 20, Especially preferably, it is a hydrogen atom or C1-C? It is an alkyl group of 10, More preferably, it is a hydrogen atom or C1-C? 6 is an alkyl group.

As imidazole compound (D), for example, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5- Hydroxymethylimidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 1-cyanomethyl-2-undecyl Midazole, 1-cyanomethyl-2-ethyl-4-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 can be used individually or in combination of 2 or more types.

The content of the imidazole compound (D) is preferably 1 part by mass or more and 25 parts by mass or less, and 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 content of an imidazole compound (D) exists in said range, the pattern and coating film obtained tend to be excellent in transparency.

It is preferable that curable resin composition of this invention contains a thiol compound (T) further. Thiol compound (T) is a compound which has a sulfanyl group (-SH) in a molecule | numerator. Especially, the compound which has two or more sulfanyl groups is preferable, and the compound which has two or more sulfanyl groups couple | bonded with the carbon atom of an aliphatic hydrocarbon structure is more preferable. There exists a tendency for a sensitivity to become high by containing a thiol compound (T) in curable resin composition of this invention.

As a thiol compound (T), for example, hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate), butanediolbis (3-sulfanyl acetate ), Ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfanyl propionate) , Trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris (3-sul Panylpropionate), pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

The content of the thiol compound (T) is preferably 10? To 100 parts by mass of the polymerization initiator (C). 90 parts by mass, more preferably 15? 70 parts by mass. When content of a thiol compound (T) exists in this range, there exists a tendency for a sensitivity to become high and developability becomes favorable.

It is preferable that curable resin composition of this invention contains a solvent (E).

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and not containing -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), ether ester Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule,- Solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

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

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

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

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

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

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

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

You may use these solvents individually or in combination of 2 or more types.

Among the solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable in view of applicability and drying properties. 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.

Content of the solvent (E) in curable resin composition becomes like this. 95 mass%, More preferably, it is 70? 95 mass%. In other words, solid content of curable resin composition becomes like this. 40 mass%, More preferably, it is 5? 30 mass%. Here, solid content means the quantity which removed the solvent (E) from curable resin composition. When content of a solvent (E) exists in the said range, there exists a tendency for the flatness of the film | membrane which applied curable resin composition to be high.

It is preferable that curable resin composition of this invention contains antioxidant (F). As antioxidant (F), it is, for example, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl Propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3) -tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylene Bis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl- 5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodiprop Cypionate, distearyl 3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5- Lis (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3k, 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, etc. IRGANOX (registered trademark) 3114 ( You may use a commercial item, such as the BASF Japan company make.

Content of antioxidant (F) is 0.1 mass part or more and 5 mass parts or less with respect to 100 mass parts of polymers (A), and 0.5 mass part or more and 3 mass parts or less are preferable. When content of antioxidant (F) is in the said range, the coating film obtained tends to be excellent in heat resistance and pencil hardness. When content of antioxidant (F) exceeds 5 mass parts, there exists a possibility that pencil hardness may fall.

Curable resin composition of this invention may contain surfactant (G). As surfactant, silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 Production).

As a fluorine type surfactant, surfactant which has a fluorocarbon chain is mentioned. Specifically, fluorine nut (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), mega pack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F552, Copper F553, Copper F554, Copper F555, Copper F556, Copper F558, Copper F559, Copper R30 (manufactured by DIC Corporation), F-Top (registered trademark) EF301, Copper EF303, Copper EF351, Copper EF352 (Mitsubishi Material Electronic Chemicals ( Ltd.), Supron (registered trademark) S381, S382, SSC101, SSC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute), and the like.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain is mentioned. Specifically, Megapack (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), etc. may be mentioned. Preferably Megapack (registered trademark) F475 is mentioned.

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

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

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

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

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

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

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

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

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

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

When the curable resin composition of this invention is used as a coating film, the average transmittance of a coating film becomes like this. Preferably it is 90% or more, More preferably, it is 95% or more. This average transmittance | permeability measures the wavelength 400-degree using a spectrophotometer with respect to the coating film whose thickness after heat-hardening (for example, 100-250 degreeC, 5 minutes-3 hours) is 3 micrometers. It is the average value when it measures on 700 nm conditions. Thereby, the coating film excellent in transparency in visible region can be provided.

Curable resin composition of this invention uses a polymer (A), a (meth) acryl compound (B), a polymerization initiator (C), an imidazole compound (D), a solvent, other additives, etc. by a conventionally well-known method as needed. It can manufacture by stirring and mixing. After mixing, the hole diameter is 0.05? It is preferable to filter by a filter of about 1.0 micrometer.

Curable resin composition of this invention can be formed as a coating film, for example by apply | coating on these board | substrates which formed board | substrates, such as a glass, a metal, a plastic, a color filter, various insulation or electrically conductive films, a drive circuit, etc., for example. It is preferable that a coating film dried and hardened | cured. Moreover, the obtained coating film can also be patterned in a desired shape and used as a pattern. In addition, you may form and use these coating films or patterns as a part of component parts, such as a display apparatus.

First, the curable resin composition of this invention is apply | coated on a board | substrate.

Application | coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Subsequently, it is preferable to dry or prebake to remove volatile components, such as a solvent. Thereby, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, 1? About 6 micrometers is illustrated.

Moreover, light, for example, a mercury lamp, the ultraviolet-ray generate | occur | produces from a light emitting diode, etc. are irradiated to the obtained uncured coating film through the mask for forming the target pattern. The shape of the mask at this time is not specifically limited, Various shapes are mentioned. Further, 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, etc. of a pattern can be adjusted suitably according to the mask size, the transmittance | permeability of a mask light transmission part, etc.

In a recent exposure machine, a band pass filter which cuts light of less than 350 nm using a filter that cuts this wavelength range, or extracts light of around 436 nm, 408 nm, and 365 nm is taken out of these wavelength ranges. It can take out selectively using, and can irradiate a parallel light beam uniformly to the whole exposure surface. At this time, in order to perform exact alignment of a mask and a board | substrate, you may use apparatuses, such as a mask aligner and a stepper.

After that, the coating film is brought into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, a non-exposed portion, to obtain a target pattern shape.

The developing method may be any of a liquid mounting method, a dipping method, a spray method, and the like. In addition, during development, the substrate may be tilted at an arbitrary angle.

As for the developing solution used for image development, the aqueous solution of an alkaline compound is preferable.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine and the like.

The concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. 10 mass%, More preferably, it is 0.03? 5 mass%.

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

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

As nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzene sulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

As cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned, for example.

The concentration of the surfactant in the alkaline developer is preferably 0.01? 10 mass%, More preferably, it is 0.05? 8 mass%, More preferably, it is 0.1? 5 mass%.

After image development, water washing may be performed and you may perform post-baking further as needed. Post-baking, for example, 150? Temperature range of 240 ℃, 10? 180 minutes is preferred.

The coating film or pattern obtained in this way is useful as a photospacer used for a liquid crystal display device, and a patternable overcoat, for example. In the case of patterning exposure to an uncured coating film, by using a hole forming photomask, holes can be formed, which is useful as an interlayer insulating film. In addition, at the time of exposing to an uncured coating film, a transparent film can be formed by performing whole surface exposure, heat hardening, or only heat hardening, without using a photomask. This transparent film is useful as an overcoat. Moreover, it can also be used for display apparatuses, such as a touch panel. Thereby, the display apparatus provided with a high quality coating film or a pattern can be manufactured with high yield.

The curable resin composition of the present invention is a material for forming various films and patterns, for example, a transparent film, a pattern, a photo spacer, an overcoat, an insulating film, a projection for forming a liquid crystal alignment, which constitute a part of a color filter and / or an array substrate, It is preferable in order to form a micro lens, a coat layer, etc. Moreover, the display apparatus provided with these color filters and / or array substrates, etc. which are equipped with these coating films or patterns as a part of its component parts, For example, a liquid crystal display device, an organic EL device, It can be used for electronic paper and the like.

Example

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

(Synthesis Example 1)

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

[Chemical Formula 9]

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

(Synthesis Example 2)

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. Heated to 70 ° C. Next, molar ratio of 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02.6] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1), 50 240 parts of: 50) was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was dripped at the flask over 4 hours using another dropping funnel. It was. After dripping of the polymerization initiator solution was complete | finished, it was kept at 70 degreeC for 4 hours, and cooled to room temperature after that, the solution of the copolymer (resin Ab) of 32.6% of solid content and acid value 110 mg-KOH / g (solid content conversion). Got. The weight average molecular weight (Mw) of obtained resin Ab was 13,400, and molecular weight distribution (Mw / Mn) was 2.50.

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

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

Calibration standard; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosso Corporation)

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

(Examples 1 to 8 and Comparative Example 1)

The components of Table 1 were mixed and the curable resin composition was obtained.

In addition, unless otherwise indicated in Table 1, a unit is "part". The containing number of a polymer (A) shows the mass part of solid content conversion.

Polymer (A); Aa; Resin Aa Obtained in Synthesis Example

Polymer (A); Ab; Resin Ab Obtained in Synthesis Example

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

Polymerization initiator (C); Ca; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure (registered trademark) OXE 01; manufactured by BASF; oxime compound)

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

Polymerization initiation aid (C1); C1a; 2- (2-naphthoylmethylene) -3-methylbenzothiazoline

Imidazole compound (D); Da; 1-benzyl-2-phenylimidazole (curazole 1B2PZ; manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[Formula 10]

Imidazole compound (D); Db; 1- (2-cyanoethyl) -2-undecylimidazole (curesol C11Z-CN; manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[Formula 11]

Imidazole compound (D); Dc; 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole (curazole 2E4MZ-CN; manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[Chemical Formula 12]

Thiol compound (T); Ta; Pentaerythritol tetrakis propionate (PEMP; manufactured by 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) -trione ( 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-ethoxyethylpropionate

Solvent (E); Ee; 3-methoxybutyl acetate

The solvent (E) is mixed so that the solid content of the curable resin composition becomes the "solid content (%)" in Table 1, and the solvent component (Ea) in the solvent (E)? The value of (Ee) shows the mass ratio in a solvent (E).

<Viscosity measurement>

About the obtained curable resin composition, the viscosity was measured using the viscometer (model; TV-30; Toki Sangyo Co., Ltd. product), respectively. The results are shown in Table 2.

<Transmittance of Curable Resin Composition>

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

<Production of coating film>

A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was washed sequentially with a neutral detergent, water, and 2-propanol, and dried. On this glass substrate, a curable resin composition is spin-coated so that the film thickness after postbaking may be set to 3.0 micrometers, and then prebaked at 90 degreeC in a hotplate for 2 minutes, and then an exposure machine (TME-150 RSK; Topcon Co., Ltd.) The coating film after prebaking was exposed by exposure amount (365 nm standard) of 100 mJ / cm <2> in air | atmosphere using manufacture, the light source; ultrahigh pressure mercury lamp). In this exposure, the light emitted from the ultra-high pressure mercury lamp was irradiated through an optical filter (UV-33; manufactured by Asahi Techno Glass Co., Ltd.). After exposure, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

<Transmittance of Coating Film>

About the obtained coating film, 400 micrometers was used using a microscopic spectrophotometer (OSP-SP200; OLYMPUS Corporation). The average transmittance (%) at 700 nm was measured. The results are shown in Table 2.

<Heat resistance>

The obtained coating film was heated in an oven for 60 minutes at 240 degreeC, the film thickness and transmittance | permeability before and after heating were measured, and the film thickness change (%) and the transmittance change (%) were calculated | required according to following Formula. In addition, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nihon Vacuum Technology Co., Ltd. product). As all are close to 100%, the change before and behind heating is small, and it means that it is excellent in heat resistance. Moreover, when the heat resistance of a 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 (μm) / film thickness before heating (μm)) × 100

&Lt; Pattern formation &gt;

A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water, and 2-propanol, and dried. On this glass substrate, curable resin composition was apply | coated by spin coating so that the film thickness of the pattern after postbaking might be set to 3 micrometers. Subsequently, the pressure reduction degree was reduced to 0.5 torr by the pressure reduction dryer (made by VCD Microtech Co., Ltd.), and it dried and formed the coating film. This coating film was prebaked at 90 degreeC in a hotplate for 2 minutes. The exposure amount of 100 mJ / cm <2> (365 nm reference | standard) in air | atmosphere, using the exposure machine (TME-150RSK; Topcon Co., Ltd. light source, ultra-high pressure mercury lamp), and the space | interval of a board | substrate and quartz glass photomask is 10 micrometers. The coating film after prebaking was exposed. In this exposure, the light emitted 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, diameters of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 A photomask having a circular transmissive portion of 20 탆 and 20 탆, the pattern having an interval of 100 탆, was formed on the same plane.

After exposure, the solution was immersed at 25 ° C. for 60 seconds with an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by washing with water, followed by post-baking at 230 ° C. for 20 minutes in an oven. Formed.

<Resolution evaluation>

The pattern obtained by the scanning electron microscope (S-4000; the Hitachi Corporation make) was observed, and the minimum line width from which the pattern was isolate | separated was made into the resolution. The results are shown in Table 2.

From the said result, it was confirmed that the coating film obtained by the curable resin composition of this invention has small change of the transmittance | permeability in a heat resistance test, and little coloring by heat processing.

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

Claims (4)

Curable resin composition containing following (A), (B), (C) and (D):
(A) An addition polymer containing the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the unsaturated compound which has an oxiranyl group.
(B) a compound having at least one group selected from the group consisting of acryloyl group and methacryloyl group
(C) polymerization initiator
(D) Compound represented by Formula (1)
[Chemical Formula 13]

[In formula (1), R <^1> is a benzyl group or C2? 5 represents a cyanoalkyl group,
R ² ? R ⁴ independently of one another is a hydrogen atom, a halogen atom, carbon atoms? 20 alkyl, phenyl, nitro or C 1? 20 acyl group, and the hydrogen atom contained in this alkyl group and this phenyl group may be substituted by the hydroxy group]. The method of claim 1,
Curable resin composition whose content of (D) is 1 mass part or more and 25 mass parts or less with respect to 100 mass parts of (A). The coating film formed of the curable resin composition of Claim 1 or 2. The display device containing the coating film of Claim 3.