KR20120134026A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to form a conic protrusion with a small diameter formed on foreign substances even if a coating film is formed on a color filter with the foreign substances of several microns. CONSTITUTION: A curable resin composition comprises: an addition polymer which comprises a unit structure which is originated from at least one kind selected from an unsaturated carboxylic acids and unsaturated carboxylic anhydride, and a unit structure originated from an unsaturated compound with an oxyranyl group; at least one kind of selected from glycidyl ether type epoxy resins and glycidyl ester type epoxy resin; and a compound indicated in chemical formula 1.

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 only the copolymer of unsaturated carboxylic acid and an aliphatic polycyclic epoxy compound as a resin component is known (patent document 1).

Japanese Unexamined Patent Publication No. 2009-149854

When a coating film is formed on the color filter in which the foreign matter of about several micrometers exists, conical protrusions are formed in the foreign matter on the coating film. If the diameter is small, the conical projection can remove the projection by polishing. However, when the diameter is large, the coating film cannot be sufficiently flattened even if the projection is removed by polishing. If a coating film that is not sufficiently flattened is used for the liquid crystal display device, it causes a display defect. With the conventionally known curable resin composition, when a coating film is formed on a color filter in which foreign matters of several micrometers exist, the diameter of the conical protrusion formed on the foreign matter was not necessarily small enough.

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

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

(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) at least one epoxy resin selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins

(C) Compound represented by formula (1)

[Formula 1]

[In formula (1), R <^1> is a hydrogen atom and C1-C. An alkyl group, a phenyl group, a benzyl group or a carbon number of 20; 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 (C) is 1 mass part or more and 25 mass parts or less with respect to 100 mass parts of (A).

[3] Curable resin composition as described in said [1] or [2] whose content of (A) is 50 mass% or more and 99 mass% or less with respect to the sum total of content of (A) and content of (B).

[4] The above-mentioned [1] which further contains a compound having at least one group selected from the group consisting of acryloyl group and methacryloyl group. Curable resin composition in any one of [3].

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

[6] A display device comprising the coating film according to the above [5].

According to the curable resin composition of this invention, even if a coating film is formed on the color filter in which the foreign material of several micrometers exists, the diameter of the conical protrusion formed on a foreign material is small. Therefore, since the coating film formed from the curable resin composition of this invention can be planarized by grinding | polishing, it becomes possible to manufacture the liquid crystal display device with few display defects.

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, the "polymer (A)" may be referred to).

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 respectively be used independently, 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 Eng., First Edition, First Printing, March 1, 1972) and the cited documents described in this document. It can be prepared with reference to.

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 It is more than mg-KOH / g 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.

The content of the polymer (A) is preferably 50? To the total amount of the content of the polymer (A) and the content of the epoxy resin (B). 99 mass%, More preferably, it is 60? 95 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.

Curable resin composition of this invention is a case where at least 1 sort (s) of epoxy resin (B) chosen from group which consists of glycidyl ether type epoxy resin and glycidyl ester type epoxy resin (hereinafter, "epoxy resin (B)"). There is).

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure and can be synthesized by reacting epichlorohydrin with phenols, polyhydric alcohols, or the like.

Specific examples of the glycidyl ether type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, and o-cresol novolac type epoxy resins. And trishydroxyphenylmethane type epoxy resins.

A glycidyl ester type epoxy resin is an epoxy resin which has a glycidyl ester structure, and is synthesize | combined by making carboxyl groups, such as a phthalic acid derivative and a fatty acid, react with epichlorohydrin.

As glycidyl ester type epoxy resin, glycidyl ester type epoxy resin derived from aromatic carboxylic acids, such as p-oxybenzoic acid, m-oxybenzoic acid, and terephthalic acid, etc. are mentioned, for example.

It is preferable that the epoxy resin (B) used for curable resin composition of this invention is an aromatic epoxy resin, and bisphenol-A epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, o-cresol novolak-type epoxy It is preferable that it is glycidyl ether type epoxy resins, such as resin and a polyphenol type epoxy resin. Especially, a bisphenol A epoxy resin is especially preferable.

Such glycidyl ether type epoxy resins can be synthesized by condensing the corresponding phenols and epichlorhydrin in the presence of strong alkalis using a conventionally known method. Such a reaction can be performed by a method conventionally known to those skilled in the art. Moreover, you may use a commercial item. For example, as a commercial item of a bisphenol-A epoxy resin, JER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (Mitsubishi Chemical Co., Ltd.) etc. can be used. As a commercial item of a bisphenol F-type epoxy resin, Epicoat 807 (made by Mitsubishi Chemical Corporation), YDF-170 (made by Toto Chemical Co., Ltd.), etc. can be used. As a commercial item of a phenol novolak-type epoxy resin, Epicoat 152, Epicoat 154 (made by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (made by Nippon Kayaku Co., Ltd.), DEN-438 (Dow Chemical Company) etc. can be used. As a commercial item of o-cresol novolak-type epoxy resin, EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (made by Nippon Kayaku Co., Ltd.), etc. can be used. . As a commercial item of a polyphenol type epoxy resin, Epicoat 1032H60, Epicoat YX-4000 (made by Mitsubishi Chemical Corporation), etc. can be used.

The epoxy equivalent of the epoxy resin (B) is preferably 100? 500 g / eq, More preferably, it is 150? 400 g / eq. The epoxy equivalent here is defined by the molecular weight of the epoxy resin per epoxy group. Epoxy equivalent can be measured, for example by the method prescribed | regulated to JISK7236.

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

Moreover, the weight average molecular weight of an epoxy resin (B) becomes like this. 10,000, more preferably 400? 6,000, more preferably 500? 4,800.

The content of the epoxy resin (B) is preferably 1? To 100 parts by mass of the polymer (A). 100 parts by mass, more preferably 5? 67 parts by mass. When content of an epoxy resin (B) exists in said range, it exists in the tendency for the flatness of a coating film to be excellent.

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

[Formula 7]

[In formula (1), R <^1> is a hydrogen atom and C1-C. An alkyl group, a phenyl group, a benzyl group or a carbon number of 20; 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? 10, More preferably, it is C1-C? 6, particularly preferably 1? 4

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 ¹ is preferably a hydrogen atom, a benzyl group or C 2? It is a cyanoalkyl group of 5, More preferably, it is a benzyl group.

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 20.

R ² ? If R <^4> is these groups, even if a coating film is formed on the color filter in which the foreign material of several micrometers exists, the diameter of the conical protrusion formed on this foreign material will become small, and also there exists a tendency which is excellent also in the heat resistance of the obtained coating film. .

As an imidazole compound (C), for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxy Oxymethyl-4-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyldi Midazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl 4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl- 2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole Etc. can be mentioned. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable. These can be used individually or in combination of 2 or more types.

Content of an imidazole compound (C) is 1 mass part or more and 25 mass parts or less with respect to 100 mass parts of polymers (A), More preferably, they are 3 mass parts or more and 20 mass parts or less. When content of an imidazole compound (C) exists in the said range, even if a coating film is formed on the color filter in which the foreign material about several micrometers exists, there exists a tendency for the diameter of the conical protrusion formed on a foreign material to become small.

The content of the imidazole compound (C) is more preferably 3 parts by mass or more and 15 parts by mass or less. When content of an imidazole compound (C) exists in this range, there exists a tendency which is also excellent in the heat resistance of the coating film obtained.

The curable resin composition of this invention has compound (D) 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.") Hereinafter, it is preferable to contain "(meth) acryl compound (D)". The coating film obtained by containing a (meth) acryl compound (D) tends to be excellent in chemical resistance.

As a (meth) acryl compound (D) 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 (D) 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 (D) 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 (D), the (meth) acryl compound (D) 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 (D) is preferably 20? To 100 parts by mass of the polymer (A). 100 parts by mass, more preferably 25? 70 parts by mass. When content of a (meth) acryl compound (D) exists in 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 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- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 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.

Curable resin composition of this invention does not contain a photoinitiator substantially. That is, in curable resin composition of this invention, content of the photoinitiator with respect to the whole composition is less than 1 mass%, for example, Preferably it is less than 0.5 mass%. As a photoinitiator, an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, etc. are mentioned.

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, and measures 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 is a polymer (A), an epoxy resin (B), and an imidazole compound (C), if necessary, a (meth) acryl compound (D), a solvent, other additives, etc. by a conventionally well-known method. It can manufacture by mixing, stirring. After mixing, the hole diameter is 0.05? It is preferable to filter by a filter of about 1.0 micrometer.

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

Glass, metal, plastic, etc. are mentioned as a board | substrate, A color filter, various insulating films or an electrically conductive film, a drive circuit, etc. may be formed on the board | substrate.

The curable resin composition of this invention can be apply | coated on a board | substrate using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

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

The coating film from which the volatile component was removed 150? At 240 ° C., 10? A coating film can be formed by performing a 120 minute postbaking.

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

Example

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

(Synthesis Example 1)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. Then 40 parts of methacrylic acid; And 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.

[Formula 8]

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). Resin Aa has the following structural units.

[Chemical Formula 9]

(Synthesis Example 2)

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. Heated to 70 ° C. Subsequently, 60 parts methacrylic acid; And 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} = 240 parts of 140 parts of 3-methoxybutyl acetate It dissolved in the solution, the solution was prepared, and the solution was dripped in the flask heated to 70 degreeC over 4 hours using the 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 hold | maintained at 70 degreeC for 4 hours, it cooled to room temperature after that, and obtained the solution of the copolymer (resin Ab) of 32.6% of solid content. The weight average molecular weight (Mw) of obtained resin Ab was 13,400, molecular weight distribution (Mw / Mn) was 2.50, and the acid value was 113.9 mg-KOH / g (acid value in terms of solid content). Resin Ab has the following structural units.

[Formula 10]

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

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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.

Unless otherwise specified in Table 1, the 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

Epoxy Resin (B): Ba: Bisphenol A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation) (acid value: 0.1 mgKOH / g, epoxy equivalent: 210 g / eq)

Imidazole compound (C): Ca: 1-benzyl-2-phenylimidazole (curazole 1B2PZ; Shikoku Kasei Kogyo Co., Ltd. product)

[Formula 11]

Imidazole Compound (C): Cb: 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole (Curazole 2E4MZ-CN; manufactured by Shikoku Chemical Co., Ltd.)

[Chemical Formula 12]

Imidazole compound (C): Cc: 2-ethyl-4-methylimidazole (curazole 2E4MZ; Shikoku Kasei Kogyo Co., Ltd. product)

[Chemical Formula 13]

(Meth) acrylic compound (D): Da: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku 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.

<Transmittance of Coating Film>

A glass substrate (# 1737; manufactured by Corning Corporation) having a width of 2 inches was washed sequentially with a neutral detergent, water, and isopropyl alcohol, and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after postbaking might be set to 2.0 micrometers, and then prebaked for 10 minutes at 90 degreeC in a clean oven. Then, it post-baked for 40 minutes at 230 degreeC, and obtained the coating film. About the obtained coating film, it used 400 micrometers using a microscopic spectrophotometer (OSP-SP200; OLYMPUS Corporation). The average transmittance (%) at 700 nm was measured. The results are shown in Table 2.

<Measurement of conical protrusions on foreign matter>

Acrylic beads having a diameter of 8 µm (trade name: Eposta YS77; manufactured by Nippon Catalyst Co., Ltd.) were dispersed in toluene to prepare a 0.01% dispersion. The dispersion liquid was apply | coated with the spin coater on the chromium thin film formed on the 15 cm square glass substrate, and the test board | substrate with which acrylic beads were dotted was obtained.

Using the slit die coater (Table Die-100 Itochu Sanki Co., Ltd. product) in the obtained curable resin composition, respectively, on the test board | substrate, on the conditions that the film thickness after hardening will be 1.5 micrometer, and it is the application | coating speed of 70 mm / sec. Applied. Then, it dried in the pressure reduction dryer (made by VCD Microtech Co., Ltd.) until the pressure reduction degree reached 0.5 torr. After prebaking at 90 degreeC for 2 minutes on a hotplate, and further drying, it post-baked at 230 degreeC for 40 minutes, and formed the coating film.

In the obtained coating film, conical protrusions were formed centering on the acrylic beads scattered on the underlying test substrate. The protrusion was observed with a polarization microscope (× 100 times), and the diameter of the outermost circumference of the Newton ring observed in a concentric manner centered on the acrylic beads was measured. The diameter of the outermost circumference was made into the diameter of the conical protrusion. The results are shown in Table 2.

<Heat resistance evaluation>

The obtained curable resin composition was apply | coated at 120 mm / sec of application | coating speed also on the conditions which the film thickness after hardening becomes 2.0 micrometer using the slit die coater (made by Table Die-100 Itochu Sangyo Co., Ltd.), respectively. Then, it dried in the pressure reduction dryer (made by VCD Microtech Co., Ltd.) until the pressure reduction degree reached 0.5 torr. After prebaking at 90 degreeC for 2 minutes on a hotplate, and further drying, it post-baked at 230 degreeC for 40 minutes, and produced the coating film. The coating film was heated in a 240 degreeC clean oven for 4 hours, and the transmittance | permeability before and behind heating was measured. The transmittance change was calculated | required from the obtained measured value according to following Formula. If the transmittance change is 92% or more, it can be judged that heat resistance is good. The results are shown in Table 2.

Permeability Change (%) = T _b / T _a × 100

[Wherein, T _b represents the transmittance before heating at 400 nm, and T _a represents the transmittance after heating at 400 nm]

From the said result, according to the curable resin composition of this invention, even if the coating film was formed on the board | substrate with a foreign material, the diameter of the conical protrusion formed on a foreign material was small. Moreover, it was confirmed that the coating film obtained from curable resin composition of this invention is high in heat resistance. This shows that the coating film obtained from the curable resin composition of this invention is useful for manufacture of the liquid crystal display device with few display defects.

According to the curable resin composition of this invention, even if a coating film is formed on the color filter in which the foreign material of several micrometers exists, the diameter of the conical protrusion formed on a foreign material is small.

Claims (6)

Curable resin composition containing following (A), (B) and (C):
(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) at least one epoxy resin selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins
(C) Compound represented by formula (1)
[Chemical Formula 14]

[In formula (1), R <^1> is a hydrogen atom and C1-C. An alkyl group, a phenyl group, a benzyl group or a carbon number of 20; 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 (C) is 1 mass part or more and 25 mass parts or less with respect to 100 mass parts of (A). 3. The method according to claim 1 or 2,
Curable resin composition whose content of (A) is 50 mass% or more and 99 mass% or less with respect to the sum total of content of (A) and content of (B). The method of claim 1,
Furthermore, curable resin composition containing the compound which has at least 1 sort (s) of group chosen from the group which consists of acryloyl group and methacryloyl group. The coating film formed of the curable resin composition of Claim 1. The display apparatus containing the coating film of Claim 5.