KR20160023555A - Epoxy(meth)acrylate compound, resin composition containing the same and cured product thereof, color filter and display device - Google Patents

Abstract

Provided are a compound having excellent transparency and high refractive index, a resin composition which comprises the compound and has little contraction after curing, and a cured product having high abrasion resistance, adhesive strength, and sufficient hardness. The compound (A) is obtained by having a reaction between (meth)acrylic acid and an epoxy resin which is obtained from a reaction among a phenolphthalein derivative, a phenol compound synthesized from an aminobenzene derivative, and epichlorohydrin. A polycarboxylic acid compound (B) is obtained from a reaction between the compound (A) and a polybasic acid anhydride (C). The resin composition of the present invention comprises the compound (A) or compound (B). Further, provided is a resin composition comprising the compound (A), a coloring agent (D), and a binder resin (E).

Description

EPOXY ACRYLATE COMPOUND, RESIN COMPOSITION CONTAINING THE SAME, AND CURED PRODUCT THEREOF, COLOR FILTER AND DISPLAY DEVICE, EPOXY (METH) ACRYLATE COMPOUND,

The present invention relates to a compound having a specific structure having a high refractive index and excellent transparency and also excellent in heat resistance and solvent resistance, a resin composition containing the same, and a cured product thereof.

BACKGROUND ART [0002] In recent years, development of a photosensitive material having high heat resistance, high refractive index, and transparency has been under development by curing with an active energy ray. In addition to high heat resistance and high refractive index, additives such as monomers and fillers are added to the photosensitive material in order to impart adhesiveness to the base material, hardness of the cured product, solubility in alkali, and the like. However, by adding these additives, it is difficult to manifest the characteristics of an organic material such as a reduction in refractive index, and it is necessary to improve the heat resistance and the refractive index of the resin itself.

Patent Document 1 discloses the use of a reaction product of o-phenylphenol glycidyl ether and (meth) acrylic acid as an optical material. However, the compound obtained by this method is a monofunctional (meth) acrylate, and the hardness and heat resistance of the cured product may be low. Further, the liquid refractive index is about 1.58.

Patent Document 2 discloses the use of a terminal acrylate ester of an ethylene oxide adduct of 2-phenylphenol as a transmissive screen material. However, this compound is a monofunctional (meth) acrylate, and the hardness and heat resistance of the cured product may be low. The refractive index of the liquid is about 1.57.

Patent Document 3 discloses the use of a resin composition containing a urethane compound obtained from phenylphenol as an optical lens sheet material.

Patent Document 4 discloses the use of a resin composition comprising a urethane compound obtained from phenylphenol and (meth) acrylate having a fluorene skeleton as an optical lens sheet material.

In Patent Document 5, it is known to use a resin composition containing a (meth) acrylate having a phenylphenol skeleton and a fluorene skeleton as an optical lens sheet material. However, there is a problem in terms of adhesion to the substrate and toughness from its rigid skeleton there was. In addition, there is no description about imparting adhesion due to carbonic acid denaturation, developing property, or patterning with an alkali developer.

Patent Document 6 discloses an epoxy resin having a 2-hydrocarbyl-3,3-bis (4-hydroxyaryl) phthalimidine skeleton, and its application to an adhesive, a paint, a coating agent, and the like is disclosed. Patent Document 7 describes a resin composition containing the epoxy resin and a carbon acid and / or a cationic polymerization catalyst, and discloses its use as a glass substitute material, an adhesive, a paint, a coating agent, and the like. Patent Document 8 also discloses an epoxy resin having a 2-hydrocarbyl-3,3-bis (4-hydroxyaryl) phthalimidine skeleton.

Japanese Patent Application Laid-Open No. 9-272707 Japanese Patent Application Laid-Open No. 5-065318 International Publication No. 2008 / 136262A1 Japanese Laid-Open Patent Publication No. 2010-265346 Japanese Patent Application Laid-Open No. 2008-094987 GB1158606A International Publication No. 2013 / 183735A1 International Publication No. 2013 / 183736A1

An object of the present invention is to provide a resin composition which is excellent in transparency and has a high refractive index by itself, and a resin composition containing the compound and which has a high adhesiveness and has a sufficient hardness.

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and found that unsaturated group-containing compounds having a specific structure and resin compositions containing such compounds solve the above problems and have completed the present invention .

That is, the present invention relates to an epoxy carboxylate compound (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having an ethylenically unsaturated group and a carboxyl group in a molecule:

(In the general formula (1), R ₁ is each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a represents the number of the substituent R ₁ , Or 2).

The present invention also relates to the above epoxy carboxylate compound (A) wherein R _{1 in the} general formula (1) is a hydrogen atom, and the compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule is (meth) acrylic acid or cinnamic acid.

The present invention also relates to a polycarboxylic acid compound (B) obtained by reacting the above epoxy carboxylate compound (A) with a polybasic acid anhydride (c).

The present invention also relates to a resin composition containing the epoxy carboxylate compound (A) or the polycarboxylic acid compound (B).

The present invention also relates to the resin composition comprising the reactive compound (C) other than the epoxy carboxylate compound (A) and the polycarboxylic acid compound (B).

The reactive compound (C) is at least one compound selected from the group consisting of (poly) ester (meth) acrylate (C-1), urethane (meth) acrylate (C- (Meth) acrylate (C-4), an alkyl (meth) acrylate or an alkylene (meth) acrylate (C-5) (C-8), a (meth) acrylamide compound (C-9), and an unsaturated polyester (C-10) having at least one functional group selected from the group consisting of (meth) acrylate ≪ / RTI > or more.

The reactive compound (C) may be a urethane (meth) acrylate (C-2), an alkyl (meth) acrylate or an alkylene (C-6). ≪ / RTI >

And the refractive index (D line, 25 ° C) is 1.52 to 1.72.

Further, the present invention relates to a resin composition containing the epoxy carboxylate compound (A), the colorant (D) and the binder resin (E).

Also, the present invention relates to the resin composition, wherein the colorant (D) is at least one selected from a zotenic dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye and an azo dye.

Further, the binder resin (E) relates to the resin composition wherein the copolymer is a copolymer of an unsaturated monomer containing a carboxyl group and an unsaturated carboxylic acid ester.

The present invention also relates to a cured product of the resin composition.

Further, the present invention relates to a color filter having the cured product.

Further, the present invention relates to a display element having the color filter.

A resin composition comprising an epoxy carboxylate compound (A) obtained by reacting an epoxy resin (a) represented by the general formula (1) of the present invention with a compound (b) having an ethylenically unsaturated group and a carboxyl group in a molecule, Alternatively, the cured product of the resin composition containing the polycarboxylic acid compound (B) obtained by further reacting the polybasic acid anhydride (c) with the epoxy carboxylate compound (A) is not only excellent in balance of heat resistance and moisture resistance, Transparency, and exhibits a high refractive index. Further, the cured product is a material having excellent mechanical properties such as toughness, heat resistance and solvent resistance, and is a film-forming material particularly excellent in adhesion to a base material and resistance to instability. The resin composition of the present invention is suitable as a material for use in an optical resist since it can develop by alkali-solubility by a polycarboxylic acid. For example, it is suitable for optical applications such as a hard coating for a display device such as a lens, an optical disk, and a liquid crystal display, a photoconductive material such as a film and an optical waveguide, and further, a display device having a color filter and a color filter.

(Mode for carrying out the invention)

The resin composition of the present invention is a resin composition comprising a compound represented by the general formula (1) (wherein R ₁ is each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms (B) having an ethylenically unsaturated group and a carboxyl group in the molecule is reacted with an epoxy resin (a) represented by the formula (a), wherein a represents the number of the substituent R ₁ and is 1 or 2, ) Or a polycarboxylic acid compound (B) obtained by further reacting an epoxy carboxylate compound (A) with a polybasic acid anhydride (c).

In the general formula (1), R ₁ is appropriately selected according to the intended use. For example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. Of these, compounds in which all of R < ₁ > are hydrogen atoms are most preferable from the viewpoint of availability of materials and the like.

In the present invention, a represents the number of substituents R ₁ and is 1 or 2.

In the present invention, the alkyl group having 1 to 6 carbon atoms may be any of linear, branched and cyclic. Preferably a methyl group, an ethyl group or a propyl group.

In the present invention, the alkoxy group having 1 to 6 carbon atoms may be any of linear, branched and cyclic. Preferably a methoxy group or an ethoxy group.

In the present invention, the halogen atom may be a chlorine atom, a bromine atom or an iodine atom.

The epoxy resin (a) represented by the general formula (1) can be obtained in accordance with, for example, the production method described in Patent Document 1. [ Further, a commercially available product (WHR-EP manufactured by Nippon Kayaku Co., Ltd .: R _{1 in the} general formula (1) is a hydrogen atom and the epoxy equivalent is 266 g / eq) can also be used.

In the epoxy resin (a), an epoxy equivalent of less than 266 g / equivalent is particularly preferable in the present invention. The reason for this is that more ethylenically unsaturated bonds can be introduced into the epoxy carboxylate compound (A) and the polycarboxylic acid compound (B), so that the resulting cured product is imparted with mechanical strength, resulting in a stronger resin.

The epoxy carboxylate compound (A) of the present invention is obtained by reacting (epoxycarboxylating) the compound (b) having the ethylenic unsaturated group and the carboxyl group in the epoxy resin (a). The polycarboxylic acid compound (B) of the present invention can be obtained by reacting the polybasic acid anhydride (c) in addition to the epoxy carboxylate compound (A) (acid addition step).

An ethylenic unsaturated group which is a reactive group of an active energy ray is introduced into the skeleton of the epoxy resin by the above epoxy carboxylatization process. Specifically, it is a reaction between an epoxy group and a carboxyl group. Examples of the compound (b) having both of the ethylenic unsaturated group and the carboxyl group include (meth) acrylic acid, crotonic acid,? -Cyanosinic acid, cinnamic acid or a compound having unsaturated group and hydroxyl group in saturated or unsaturated And a compound obtained by reacting a dibasic acid.

Examples of the compound obtained by reacting a compound having both an unsaturated group and a hydroxyl group with a saturated or unsaturated dibasic acid include a (meth) acrylate derivative having one hydroxyl group in one molecule and a saturated or unsaturated dibasic acid anhydride And a half ester obtained by an equimolar reaction. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate are reacted with maleic anhydride, Phthalic acid, partially or fully hydrogenated phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b), the compound (b) is preferably a monocarbon acid. When a monocarbonic acid and a polycarboxylic acid are used in combination, the ratio of the molar amount of the monocarboxylic acid / the molar amount of the polycarboxylic acid is preferably 15 or more. As the compound (b), (meth) acrylic acid or cinnamic acid is preferable in view of sensitivity to an active energy ray when it is a resin composition.

The charging ratio of the epoxy resin (a) and the compound (b) in this reaction is appropriately changed depending on the use. That is, when all the epoxy groups are carboxylated, there is no unreacted epoxy group, so the storage stability of the epoxy carboxylate compound (A) is high. In this case, only the reactivity due to the introduced double bond is used in the curing reaction.

The amount of the epoxy resin (a) and the amount of the compound (b) to be added is preferably such that the amount of the carboxyl group of the compound (b) is from 0.90 to 1 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a) in the epoxycarboxylation step in the case where the epoxy group is not left. To 1.20 equivalents are preferred. In this range, since the unreacted epoxy group remains or does not remain, the resin does not gel in the acid addition step and the storage stability of the resin is good. When the amount of the compound (b) to be added is within this range, the epoxy group remaining in the compound (a) is small and the stability of the resin is improved.

On the other hand, by reducing the amount of the compound (b) to leave an unreacted epoxy group, the reaction by the introduced unsaturated bond and the reaction by the remaining epoxy group (for example, a polymerization reaction by a light- ) Can be used in combination for curing. In this case, adhesion to a metal material or the like is improved and curing shrinkage is reduced. However, attention must be paid to the preservation and production conditions of the epoxy carboxylate compound.

When leaving an epoxy group, 0.20 to 0.90 equivalent of the carboxyl group of the compound (b) is added to 1 equivalent of the epoxy group of the epoxy resin (a). Within this range, the effect of complex curing is exerted. Further, in the case of leaving an epoxy group, it is necessary to pay attention to the gelation during the subsequent reaction and the stability with time of the epoxy carboxylate compound (A). In the case of using as the polycarboxylic acid compound (B) through an acid addition step described later, it is preferable not to leave an epoxy group. That is, when a large amount of epoxy groups remain, they react with the introduced carboxyl groups, and the storage stability is particularly deteriorated.

Epoxycarboxylation process is diluted with solvent or non-solvent. When a solvent is used, the solvent is not particularly limited as long as it does not affect the reaction. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; petroleum ether, white gasoline, solvent naphtha, Ester solvents, ether solvents, ketone solvents and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Mono or polyalkylene glycol monoalkyl ethers such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether monoacetate Polycarboxylic acid alkyl esters such as monoacetates, dialkyl glutarates, dialkyl succinates, and dialkyl adipates; and the like.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

In addition, the late reactive compound (C) and the like may be used as the solvent in the epoxy carboxylation step. These solvents may be used alone or in combination. In this case, it can be used as it is as the resin composition of the present invention.

In the epoxycarboxylation process, a catalyst may be used to promote the reaction. The amount of the catalyst to be used is about 0.1 to 10 mass% with respect to the total amount of the reactants. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate , And basic catalysts such as zirconium octanoate.

The reaction temperature of the epoxycarboxylation process is 60 to 150 캜. The reaction time is preferably 5 to 60 hours. As the thermal polymerization inhibitor of the epoxy carboxylation process, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di- -4-hydroxytoluene, and the like.

In the epoxy carboxylation step, the acid value (in accordance with JIS K5601-2-1: 1999) of the sample is 3 mgKOH / g or less, preferably 2 mgKOH / g or less As the end point.

Next, the acid adding process will be described. The acid addition process is intended to obtain a polycarboxylic acid compound (B) having a carboxyl group introduced via an ester bond by reacting a polybasic acid anhydride (c) with a hydroxyl group generated by an epoxy carboxylation process.

The polybasic acid anhydride (c) is not particularly limited as long as it is a compound having an acid anhydride structure in the molecule. Examples of the anionic surfactant include anhydrous succinic acid, anhydrous phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl- Hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride are preferred.

The acid addition step may be carried out by adding the polybasic acid anhydride (c) to the reaction liquid of the epoxy carboxylation step. The amount of the polybasic acid anhydride (c) to be added is appropriately changed depending on the application.

However, when the polycarboxylic acid compound (B) used in the resin composition of the present invention is used as an alkali development type resist, the solid acid value of the finally obtained polycarboxylic acid compound (B) (JIS K5601-2-1: 1999 (C) of 40 to 100 mg · KOH / g, preferably 60 to 90 mg · KOH / g, based on the weight of the polybasic acid anhydride. When the solid acid value is smaller than this range, the developability of the aqueous alkali solution of the resin composition is markedly lowered, and in the worst case, development is impossible. When the solid acid value exceeds the upper limit, the polybasic acid anhydride (c) becomes excessive relative to the reaction point, unreacted polybasic acid anhydride (c) remains in the composition and the developing property becomes too high, .

In the acid addition process, a catalyst is preferably used to promote the reaction. The amount of the catalyst to be used is preferably about 0.1 to 10 mass% with respect to the total amount of the reactants. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate , And zirconium octanoate.

The reaction temperature of the acid addition process is 60 to 150 占 폚. The reaction time is preferably 5 to 60 hours.

The acid addition process is diluted with solvent or non-solvent. When a solvent is used, the solvent is not particularly limited as long as it does not affect the reaction. In the case where a solvent is used in the epoxy carboxylatization step of the previous step, the solvent may be added to the acid addition step without removing the solvent if the solvent does not affect the acid addition step.

As the solvent, there can be mentioned the same solvent as in the epoxycarboxylation process.

In addition, as the solvent in the acid addition step, the late reactive compound (C) and the like may be used. These solvents may be used alone or in combination. In this case, it can be used as it is as the resin composition of the present invention. As the thermal polymerization inhibitor in the acid addition step, the same epoxy carboxylatization process can be used. The acid addition step has an acid value of the reactant in the range of plus or minus 10% of the acid value set in accordance with the intended use while properly sampling.

As a result, the compound (A) or (B) of the present invention having a high refractive index and excellent transparency can be obtained.

The resin composition of the present invention contains the compound (A) or (B) of the present invention, but may contain other reactive compound (C) other than the compound (A) or (B), if necessary.

In the present invention, the reactive compound (C) refers to a compound capable of reacting with an active energy ray. Specific examples include (poly) ester (meth) acrylate (C-1), urethane (meth) acrylate (C-2), epoxy (meth) acrylate (Meth) acrylate having an alicyclic structure, (meth) acrylate having an alicyclic structure (C-4), alkyl (meth) acrylate or alkylene (C-7), a maleimide group-containing compound (C-8), a (meth) acrylamide compound (C-9) and an unsaturated polyester (C-10). .

Examples of the (poly) ester (meth) acrylate (C-1) usable in combination with the resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / Monofunctional (poly) ester (meth) acrylates such as phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate and caprolactone modified tetrahydrofurfuryl (meth) acrylate;

Di (meth) acrylates such as hydroxypivalic acid esters neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxy diacid ester neopentyl glycol di (meth) acrylate and epichlorohydrin modified phthalic acid di (meth) ) Ester (meth) acrylates;

Mono-, di- or tri (meth) acrylate of a triol obtained by adding 1 mol or more of a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone to 1 mol of trimethylolpropane or glycerin .

Further, a mono, di-triol of triol obtained by adding 1 mol or more of a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane Or triol monomers obtained by adding tetra (meth) acrylate, cyclic lactone compounds such as? -Caprolactone,? -Butyrolactone, and? -Valerolactone in an amount of 1 mol or more per mole of dipentaerythritol, (Meth) acrylate or poly (meth) acrylate of a polyhydric alcohol such as triol, tetraol, pentanol or hexanol of a (meth) acrylate.

Further, it is also possible to use a diol component such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, There may be mentioned polybasic acids such as acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimeric acid, sebacic acid, azelaic acid and 5-sodium sulfoisophthalic acid, (Meth) acrylates of polyester polyols;

(Poly) ester (meth) acrylate such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of the diol component, a polybasic acid and anhydrides thereof, and? -Caprolactone,? -Butyrolactone, ) Acrylates, but the present invention is not limited thereto.

(C-2) having at least one (meth) acryloyloxy group and an isocyanate compound (C-2) having at least one (meth) acryloyloxy group can be used in combination with the urethane (meth) - (b) is a generic term of (meth) acrylate.

Specific examples of the hydroxy compound (C-2-a) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate compound having various hydroxyl groups such as acrylate, acrylate, pentaerythritol tri (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate compound and? -Caprolactone.

Specific examples of the isocyanate compound (C-2-) include, for example, p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylylene diisocyanate, m-xylylenediisocyanate, 2,4-tolylene diisocyanate, , Aromatic diisocyanates such as 6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and naphthalene diisocyanate;

Aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate and lysine diisocyanate;

Polyisocyanates such as at least one burette of an isocyanate monomer or an isocyanate compound obtained by trimerizing the diisocyanate compound;

And polyisocyanates obtained by the urethane reaction between the isocyanate compound and the polyol compound.

The epoxy (meth) acrylate (C-3) that can be used in combination with the resin composition of the present invention is a generic name of (meth) acrylates obtained by reacting (meth) acrylic acid with an epoxy resin containing at least one epoxy group. Specific examples of the epoxy resin as a raw material of the epoxy (meth) acrylate include phenyl diglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether and resorcinol diglycidyl ether;

Bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane A bisphenol-type epoxy compound such as an epoxy compound;

Hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- Hydrogenated bisphenol-type epoxy compounds such as epoxy compounds of hexafluoropropane;

Halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resin and brominated bisphenol-F type epoxy resin;

Alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compounds;

Aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether and diethylene glycol diglycidyl ether;

Polysulfide diglycidyl ether compounds such as polysulfide diglycidyl ether;

Phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenyl methane type epoxy resin, dicyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol-A type novolak type epoxy resin, naphthalene skeleton Containing epoxy resin, heterocyclic epoxy resin, and the like.

Examples of the (poly) ether (meth) acrylate (C-4) usable in combination with the resin composition of the present invention include butoxy ethyl (meth) acrylate, butoxy triethylene glycol (meth) (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate (Poly) ether (meth) acrylates such as nonylphenoxy polyethylene glycol (meth) acrylate.

Further, alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and polytetramethylene glycol di Methacrylate;

A polyhydric alcohol compound such as a hydrocarbon polyol such as a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol, Polyfunctional (meth) acrylates derived from (meth) acrylic acid;

(Meth) acrylates of diols obtained by adding 1 mol or more of a cyclic ether such as ethylene oxide, propylene oxide or butylene oxide to 1 mol of neopentyl glycol.

Further, di (meth) acrylates of alkylene oxide-modified products of bisphenols such as bisphenol A, bisphenol F, and bisphenol S;

Alkylene oxide-modified di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S;

Mono-, di- or tri (meth) acrylates of triols obtained by adding trimethylol propane or a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to at least 1 mol of glycerin per mole of ethylene oxide;

.

Furthermore, mono, di-tri or tetra (meth) acrylate of a triol in which 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide is added to 1 mol of pentaerythritol or ditrimethylol propane, Rate;

(Poly) ether (meth) acrylate such as hexaol tri (meth) acrylate having 1 mole or more of ethylene oxide, propylene oxide or butylen oxide added to 1 mole of dipentaerythritol, Acrylates and the like.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) usable in the resin composition of the present invention include octyl (meth) acrylate, isooctyl (meth) (Meth) acrylate, and dodecyl (meth) acrylate.

(Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (Meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, And di (meth) acrylates of diols.

(Meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter referred to as "poly" as a collective polyfunctional group such as di-, tri- or tetra), glycerin Mono- or poly (meth) acrylates of pentaerythritol, mono- or poly (meth) acrylates of ditrimethylolpropane, mono- or poly (meth) acrylates of dipentaerythritol, (Meth) acrylate, and mono- or poly (meth) acrylates of polyhydric alcohols such as tetraol and hexanol.

(Meth) acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl have.

Examples of the (meth) acrylate (C-6) having an aromatic ring which can be used in combination with the resin composition of the present invention include phenyl (meth) acrylate, benzyl (meth) acrylate, Monofunctional (meth) acrylates such as a terminal acrylic acid ester adduct of water (for example, OPP-1 manufactured by Nippon Kayaku Co., Ltd.);

Di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, but are not limited thereto.

Examples of the (meth) acrylate (C-7) having an alicyclic structure that can be used in combination with the resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl Monofunctional (meth) acrylates having an alicyclic structure such as acrylate and dicyclopentenyl (meth) acrylate;

Di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F;

Polyfunctional (meth) acrylates having a cyclic structure such as tricyclodecane dimethylol (meth) acrylate;

And alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafluoropropyl (meth) acrylate. However, the present invention is not limited thereto.

Examples of the compound having a (meth) acryloyl group that can be used in combination with the resin composition of the present invention include compounds other than the above-mentioned compounds such as a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) Poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a (meth) acrylate polymer with (meth) acrylic acid;

(Meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate;

Isocyanur (meth) acrylate such as tris (meth) acryloxyethyl isocyanurate;

(Meth) acrylates having a polysiloxane skeleton;

Polybutadiene (meth) acrylate, and melamine (meth) acrylate.

Examples of the maleimide group-containing compound (C-8) which can be used in combination with the resin composition of the present invention include N, N-butyl maleimide, N-hexyl maleimide, 2-maleimide ethyl- Monofunctional aliphatic maleimides such as diethyl-propyl carbonate, N-ethyl- (2-maleimideethyl) carbamate;

Cyclohexylmaleimide and the like; alicyclic maleimide maleimides such as N-cyclohexylmaleimide;

Aliphatic bismaleimides such as N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidepropyl) ether and bis (2-maleimideethyl) carbonate;

Alicyclic bismaleimides such as 1,4-dimaleimidocyclohexane and isophorone bis urethane bis (N-ethyl maleimide);

A maleimide compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, a maleimide compound such as maleimide compound by esterification of maleimide caproic acid with tetraethylene oxide adduct of pentaerythritol, (Poly) ester (poly) maleimide compound obtained by esterifying a poly (poly) ol, and the like, but the present invention is not limited thereto.

Examples of the (meth) acrylamide compound (C-9) usable in combination with the resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N- ;

And polyfunctional (meth) acrylamides such as methylene bis (meth) acrylamide.

Examples of the unsaturated polyester (C-10) usable in combination with the resin composition of the present invention include fumaric acid esters such as dimethyl maleate and diethyl maleate;

Maleic acid, maleic acid, fumaric acid and the like and a polyhydric alcohol.

The reactive compound (C) usable in the resin composition of the present invention is preferably (C-2), (C-5) and (C-6), particularly preferably (C-5).

The proportion of the compound (A) or (B) of the present invention and the reactive compound (C) in the resin composition containing the reactive compound (C) (Unit: mass%), preferably (A) or (B) :( C) = 20: 80 to 80:20.

The resin composition of the present invention easily cures by an active energy ray. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron beams. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable in view of the suitable use of the present invention.

The refractive index (D line, 25 캜) of the resin composition of the present invention can be easily adjusted. A range of refractive index (D line, 25 DEG C) of 1.52 to 1.72 is widely used as an optical material.

The cured product of the resin composition of the present invention means that the resin composition of the present invention is irradiated with an active energy ray to be cured.

For the purpose of making the resin composition of the present invention suitable for various uses, other components may be added at an upper limit of 90 mass% in the resin composition. As other components, a polymerization initiator, a solvent, a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, a defoaming agent, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, . Other components that can be used are illustrated below.

Examples of the radical type photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether;

Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1- Acetophenones such as hexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one;

Anthraquinones such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone;

Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone;

Acetal such as 2,2-dimethoxy-2-phenylacetophenone and phenyl (?,? - dimethoxybenzyl) ketone;

Benzophenones such as benzophenone, 4,4'-thiobis (2-methyl-1,3-benzenediol), and 4,4'-bismethylaminobenzophenone;

2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and other known radical-type photopolymerization initiators.

In addition, an azo-based initiator such as azobisisobutyronitrile and a peroxide-based radical-type initiator that responds to heat such as benzoyl peroxide may be used together. The initiator may be used alone or in combination of two or more.

As the solvent, there can be enumerated the same solvents as the epoxycarboxylation step and the acid addition step. These solvents may be used alone or in combination.

The non-reactive compound is a liquid or solid oligomer or resin having low reactivity or no reactivity, and may be a (meth) acrylic acid alkyl copolymer, an epoxy resin, a liquid polybutadiene, a dicyclopentadiene derivative, a saturated polyester oligomer, But are not limited to, resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (DAP resins), petroleum resins, rosin resins, fluoric oligomers, and silicone oligomers.

Examples of the inorganic filler include inorganic fillers such as silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, titanium oxide, zirconium oxide, talc, kaolin clay, calcined clay, zinc oxide, Alumina, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like. These inorganic fillers may have a functional group such as a halogen group, an epoxy group, a hydroxyl group or a thiol group by a method such as adding a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, You may.

Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluorine resin, nylon 12, Nylon 6/66, phenol resin, epoxy resin, urethane resin, and polyimide resin.

Examples of the silane coupling agent include silane coupling agents such as? -Glycidoxypropyltrimethoxysilane or? -Chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl-1-butyl) bis (Ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) ethylene titanate, and other titanate-based coupling agents;

Aluminum-based coupling agents such as acetal-alkoxy aluminum diisopropylate;

And zirconium-based coupling agents such as acetylacetone-zirconium complexes.

The tackifier, defoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant and dye which can be used in the resin composition of the present invention are not particularly limited as far as they do not impair the curability and the resin properties, Can be used.

In order to obtain the resin composition of the present invention, the above components may be mixed, and the order and method of mixing are not particularly limited.

The resin composition of the present invention also includes a colored resin composition containing the compound (A), the colorant (D) and the binder resin (E) of the present invention.

The content of the compound (A) of the present invention in the colored resin composition of the present invention is usually 0.5 to 99 parts by mass, and preferably 5 to 50 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition.

The coloring agent (D) in the present invention can appropriately select the color or the material according to the use of a color filter or the like. Specific examples of the coloring agent include pigments, dyes and natural pigments, which may be used alone or in combination of two or more. Among them, at least one kind selected from the group consisting of pigments and dyes is preferable in that pixels having high luminance, contrast and color purity are obtained.

Specific examples of the organic pigments include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Green 7 , CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150 , CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like. Preferable specific examples of the inorganic pigments include carbon black, titanium black and the like.

As a pigment, a rake pigment is also preferable, and specifically, a rake of a triarylmethane dye or a zanthene dye with an isopoly acid or a heteropoly acid can be mentioned. The triarylmethane lake pigment is disclosed, for example, in JP-A-2007-186043. Zanthane lake pigments are disclosed in, for example, Japanese Laid-Open Patent Publication No. 2010-191304.

As the dyes, there are preferably used dyestuff dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes and azo dyes. More specifically, Japanese Laid-Open Patent Publication Nos. 2010-32999, 2010-254964, 2011-138094, International Publication No. 10/123071 pamphlet, Japanese Laid-Open Patent Publication No. 2011-116803 , Japanese Laid-Open Patent Publication No. 2011-117995, Japanese Laid-Open Patent Publication No. 2011-133844, Japanese Laid-Open Patent Publication No. 2011-174987, and the like.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying the surface of the particle with a resin, if desired. Further, the organic pigment can be used by finely grinding primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. 08-179111 can be adopted.

In the present invention, when a pigment is used as a coloring agent, a dispersing agent and a dispersing agent may be used together, if necessary. As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic, and nonionic ones can be used, but a polymer dispersing agent is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like.

These dispersants are commercially available. Disperbyk-161, Disperbyk-1, etc., as urethane dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 and BYK- LPN21324 (manufactured by BYK) 162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (manufactured by BYK), SOLSPERSE 76500 (manufactured by Lubrizol) AJISPER PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a polyester dispersant such as Soluspus 24000 (Lubrizol Co., Ltd.) ), And the like.

Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

The content of the colorant (D) is usually 0.01 to 70 parts by mass, preferably 0.5 to 50 parts by mass, more preferably 1.0 to 40 parts by mass, relative to 100 parts by mass of the total solid content of the colored resin composition of the present invention Range is more preferable.

In the present invention, the binder resin (E) functions as a dispersant and a dispersing aid because of the dispersion stability at the time of dispersing the colorant (D). When the colored resin composition is used in the photolithography method, it is preferable that the binder resin (E) and the colorant (D) are soluble in an alkaline developer used in a developing process at the time of producing a color filter. In order to form a good fine pattern, it is preferable that the binder resin (E) has sufficient curing properties with a photopolymerization initiator, a photopolymerizable monomer and the like. Further, the binder resin (E) is selected so as to have good compatibility with the constituent materials such as a colorant compound, a photopolymerization initiator, a photopolymerizable monomer, a pigment dispersion and the like, and does not cause precipitation or aggregation of the colored resin composition. When the colored resin composition is used in the ink-jet method, the binder resin (E) having good compatibility with other constituent materials may be selected because alkali solubility is not particularly required.

As the binder resin (E), a known resin can be used, but preferably an ethylenically unsaturated monomer having at least one carboxyl group or a hydroxyl group, or an ethylenically unsaturated monomer having an aliphatic hydrocarbon group or other copolymerizable aromatic hydrocarbon group And the like. Further, those having an epoxy group on the side chain or terminal thereof, or an epoxy acrylate resin to which an acrylate is added may also be used. These monomers and the like may be used singly or in combination of two or more kinds.

Examples of the carboxyl group-containing unsaturated monomer which can be used as a raw material for the binder resin include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, ethacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

(Meth) acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and 2-acryloyloxyethyl- 2-hydroxyethyl phthalic acid and the like. These ethylenically unsaturated monomers having a carboxyl group can be used singly or in combination of two or more kinds.

Examples of the hydroxyl group-containing unsaturated monomer that can be used as a raw material of the binder resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (Meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (Meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono Methacrylate, polypropylene Alkylene glycol mono (meth) acrylate and poly - and the like (ethylene glycol-propylene glycol) monomethacrylate, such as the hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate. These ethylenically unsaturated monomers having hydroxyl groups may be used alone or in combination of two or more.

Examples of the unsaturated monomer other than the above that can be used as a raw material of the binder resin include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, Aromatic vinyl compounds such as chlorostyrene, p-chlorostyrene, and p-methoxystyrene;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, para-cumylphenoxyethylene glycol (meth) (Meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate and phenoxyethyl (meth) And the like;

(Meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl Acrylate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, pentyl (Meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Alicyclic skeletons such as methyl (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid and t-butylcyclohexyl (meth) acrylate;

Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and poly (ethylene glycol-propylene glycol) monomethacrylate;

Acrylate, methoxypolyethylene glycol monomethacrylate, lauroxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolypropylene glycol mono Alkyl (meth) acrylates such as acrylate and allyloxypolyethylene glycol polypropylene glycol mono (meth) acrylate;

Unsaturated carboxylic acid amides such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl methacrylate, 2-aminopropyl methacrylate, 3-aminopropyl methacrylate and 3- Alkyl esters;

(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl Unsaturated carboxylic acid glycidyl esters such as glycidyl ether;

Carbonic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and vinylidene cyanide;

(Meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- Unsaturated amides or unsaturated amides such as N- (2-hydroxyethyl) methacrylamide and maleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

And a monoacryloyl group or mono-methacryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly- And the like. These unsaturated monomers may be used alone or in combination of two or more.

In the case of producing a binder resin (copolymer), a polymerization initiator is used. Specific examples of the polymerization initiator used in the synthesis of the copolymer herein include α, α'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile) t-butyl peroctoate, di-t-butyl peroxide benzoyl methyl ethyl ketone peroxide, and the like. The proportion of the polymerization initiator to be used is 0.01 to 25 parts by mass based on 100 parts by mass of the total monomers used in the synthesis of the copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent, but a monomer having sufficient solubility to monofunctional monomers and polymerization initiators to be used is used. Examples of the organic solvent usable for the production of the binder resin include the same organic solvents as those contained in the colored resin composition of the present invention described below.

The reaction temperature at the time of synthesizing the copolymer is preferably from 50 to 120 캜, particularly preferably from 80 to 100 캜. The reaction time is preferably 1 to 60 hours, more preferably 3 to 20 hours. The preferable acid value of the copolymer is 10 to 300 (mg · KOH / g), and the preferred hydroxyl value is 10 to 200 (mg · KOH / g). When the acid value or the hydroxyl value is less than 10, developability is deteriorated. The weight average molecular weight (Mw) of the copolymer is preferably 2000 to 400000, more preferably 3000 to 100000. When the weight average molecular weight is less than 2000 or more than 400000, the sensitivity and developability deteriorate. In the present invention, the acid value means a value measured in accordance with JIS K-2501, and the hydroxyl value means a value measured according to JIS K-1557. The weight average molecular weight refers to a value calculated in terms of polystyrene on the basis of measurement results of GPC (gel permeation chromatography).

Further, a polymer having an unsaturated double bond introduced into the side chain of the copolymer is also useful as a binder resin. For example, it is possible to use an acrylate or glycidyl ester having an alcoholic hydroxyl group such as hydroxyethyl acrylate in a maleic anhydride moiety of a copolymer with styrene, vinyl phenol, acrylic acid, acrylic acid ester, acrylamide and the like copolymerizable with maleic anhydride A compound obtained by reacting an acrylate having an epoxy group such as methacrylate and the like and a compound obtained by reacting an acrylic acid or an acrylic acid ester with an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate, And the like. (Commercially available from Shin-Nakamura Chemical Co., Ltd.), ACA-200M (manufactured by Daicel Chemical Industries, Ltd.), ORGA-3060 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AX3- (Manufactured by Nippon Kayaku), UXE-3000 (manufactured by Nippon Kayaku), ZGA-287H (manufactured by Nippon Kayaku), TCR-1338H (manufactured by Nippon Kayaku), ZXR- 1772H (manufactured by Nippon Kayaku), ZFR-1401H (manufactured by Nippon Kayaku) and ZCR-1642H (manufactured by Nippon Kayaku) can also be used as a binder resin.

The binder resin (E) may be used alone or in combination of two or more of them in the colored resin composition of the present invention.

The binder resin (E) usable in the resin composition of the present invention is preferably a copolymer of the above-mentioned unsaturated carboxyl group-containing monomer and the above unsaturated carboxylic acid esters. As such a copolymer, for example, PSY-C1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is available on the market.

The content of the binder resin (E) in the colored resin composition of the present invention is usually 0.5 to 99 parts by mass, and preferably 5 to 50 parts by mass based on 100 parts by mass of the total solid content of the colored resin composition. When the content of the binder resin (E) is less than 0.5 parts by mass, alkali developability is lowered, and surface contamination or film remaining in a region other than a portion where a pixel is formed may occur.

The colored resin composition for a color filter of the present invention may be used in combination with an organic solvent for the purpose of lowering the viscosity of the colored resin composition and improving workability upon application of the colored resin composition. As the organic solvent, those having a sufficient dissolving power to the binder resin, the photopolymerization initiator and the like which are the constituent components of the colored resin composition and having sufficient solubility to the monofunctional monomers and polymerization initiators used for the synthesis of the binder resin can be preferably used. In addition, when the pigment dispersion is prepared, those capable of maintaining the dispersion stability can also be preferably used.

Specific examples of the organic solvent contained in the colored resin composition of the present invention include benzenes such as benzene, toluene and xylene;

Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve;

Cellosolve acetate esters such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate;

Propylene glycol monoalkyl ether acetic acid esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate;

Propionic acid esters such as methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate;

Lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate;

Diethylene glycol such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

Acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate;

Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane;

Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone;

And alcohols such as methanol, ethanol, butanol, isopropyl alcohol, diacetone alcohol and benzyl alcohol, but are not limited thereto.

The organic solvent may be used alone or in combination of two or more in the colored resin composition of the present invention. The amount of the organic solvent used in the colored resin composition of the present invention is usually 10000 parts by mass or less, preferably 100 to 1000 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition.

The colored resin composition of the present invention may contain a photopolymerization initiator and / or a curing accelerator. As the photopolymerization initiator that the colored resin composition can contain, it is preferable that the photopolymerization initiator has sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source, and a radical polymerizable photoradical initiator, Generator, and the like can be used. Further, in order to perform curing with a lower exposure energy, a component of a polymerization promoter called a sensitizer can be used in combination. Specific examples of the photopolymerization initiator include esters of benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzoyl benzoic acid, benzoyl benzoic acid, 4- Benzoyl-4'-methyldiphenylsulfide, benzyldimethylketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethyl 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxynaphthoic acid, Hydroxy-2-methylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- -1,2,4-bis (trichloro Tri (trichloromethyl) -1,3,5-s-triazine, 2, 3, 5-tetramethyl- 4-bis (tribromomethyl) -6- (4'-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) 5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid Dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane- Acetate, 4,4'-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P- Dimethylaminobenzoic acid ethyl ester, 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, diazonaphthoquinone- KAYACURE DMBI, Kaya Cure BDMK, Kaya Cure BP-100, Kaya Cure BMBI, Kaya Cure DETX-S, Kaya Cure EPA IRGACURE 907, Irgacure 369, Irgacure 379EG, Irgacure OXE-01, Irgacure OME-01, and Irgacure OME-01, all of which are manufactured by Nippon Kayaku Co., Ltd., DAROCURE 1173, STR-110, STR-1 (all available from BASF Japan), Irgacure OXE-02, Irgacure PAG103 (all manufactured by BASF Japan), TME-triazine (manufactured by Sanwa Chemical), biimidazole ), But the present invention is not limited thereto.

The photopolymerization initiator may be used alone or in combination with two or more of them to the colored resin composition of the present invention. The content of the photopolymerization initiator is usually 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition.

The curing accelerator which can be contained in the colored resin composition for a color filter of the present invention is a reaction catalyst for accelerating ion curing and is, for example, an N-containing heterocyclic compound such as primary to tertiary amines or imidazoles, Acid anhydrides and the like.

Specific examples of the amine include triethylamine, triethanolamine, KAYAHARD A-A, KAYABOND C-100, Kayabond C-200S and Kayabond C-300S of Nippon Kayaku.

Specific examples of the imidazole include CUREZOL 2MZ-H, Curezol C11Z, Curezol C17Z, Curezol 1,2DMZ, Curezol 2E4MZ, Curezol 2PZ, Curezol 2P4MZ, Curezol 1B2MZ, CN, Curezol 2PZ-CN, Curezol C11Z-CNS, Curezol 2PZCNS-PW, Curezol 2MZ-A, Curezol C11Z-CN, PW, Cure Sol TBZ, Cure Sol 2PZL-T, Cure Sol 2P-OK, Cure Sol 2PHZ-PW, Cure Sol 2P4MZ-A, .

Specific examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous pyromellitic acid, biphenyltetracarboxylic acid dianhydride, and Kaya hard MCD manufactured by Nippon Kayaku Co., Ltd. Of these, imidazoles are preferable as the curing accelerator, and Cure Sol 1B2PZ, Cure Sol 2PZ, Cure Sol 1B2MZ and Cure Sol 2E4MZ are more preferable in reactivity.

The content of the curing accelerator is usually 0.01 to 50 parts by mass, preferably 0.05 to 20 parts by mass based on 100 parts by mass of the total solid content of the colored resin composition. If the content of the curing accelerator is less than 0.01 part by mass, the curability may be lowered, and if it exceeds 50 parts by mass, the storage stability may deteriorate.

When the solubility of the coloring agent (D) in the resin component is low, the dispersing agent and the dispersion aid may be used in combination. The dispersing agent or the like may be a pigment dispersing agent, a resin dispersing agent or a surfactant having good adsorbability to the coloring matter do. As the pigment dispersant, a method of mixing a sulfonic acid or a metal salt thereof with a coloring matter or a method of mixing a substituted amino methyl derivative is generally known. As the resinous dispersing agent, nonpolar nonionic systems may be used, but polymeric resins having acid value, amine value, or the like that impart good pigment adsorption properties are generally used, and acrylic resin, polyurethane resin, polycarboxylic acid, polyamide resin, . Examples of commercially available resinous dispersants include ED211 (manufactured by Cusmotocase), Ajisper PB821 (manufactured by Ajinomoto Fine Techno), Solsperus 71000 (manufactured by Avicia), Disperbyk-2001 (manufactured by Big Chem Japan) .

When an acid dye or a basic dye is used, an organic amine compound (for example, n-propylamine, ethylhexylpropionate, or the like) is reacted with the dye to modify the dye into an amine salt dye, There is known a method in which an organic amine compound (s) is reacted with a dye having a sulfonamide group or the like to make it soluble in an organic solvent and then used in combination with an organic solvent. These amine-modified dyes can also be used in combination with the colored resin composition of the present invention. Examples of the amine-denatable dyes include color dyes such as Solvent Blue 2, 3, 4, 5, 6, 23, 35, 36, 37, 38, 43, 48, 58, 59, 67, 70, 98, 102, 104;

Basic Blue 7;

Acid Blue 80, 83, 90;

Solvent Violet 8, 9 as a violet dye;

Violet 4, 5, 14;

Basic violet 10, and the like.

The colored resin composition of the present invention is produced by mixing and stirring the compound (A), the colorant (D), the binder resin (E), and other optional additives with a dissolver or a homomixer. When the coloring agent (D) is a pigment or a dye having a low solubility, the dispersion is made into a dispersion by a dispersing machine such as a paint shaker using a suitable dispersing agent, and then the compound (A), the dispersing agent and the binder resin (E) To obtain a composition.

In the colored resin composition of the present invention, various additives such as fillers, surfactants, thermal polymerization inhibitors, adhesion promoters, antioxidants, ultraviolet absorbers, antiflocculants and the like may be further added, if necessary. Further, the colored resin composition of the present invention may be subjected to microfiltration with a filter or the like to remove foreign matter or the like after its preparation.

As a method for producing a colored cured film for a color filter using the colored resin composition of the present invention (hereinafter, simply referred to as a "colored cured film"), a photolithography method and an inkjet method are mainly used, And the latter does not necessarily require a photopolymerization initiator, and a thermosetting colored resin composition containing a curing accelerator is used.

Further, for example, when the colored resin composition of the present invention is used in an ink-jet method or the like, a thermal polymerization initiator may be used in combination with the photopolymerization initiator. Examples of the thermal polymerization initiator include azo-based compounds and organic peroxide-based ones. Examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) 2'-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate and the like.

When a thermal polymerization initiator is used in combination, the amount of the total amount of the photopolymerization initiator and the thermal polymerization initiator falls within the range of the content of the above photopolymerization initiator.

Next, a method for preparing a colored hardened film from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is coated on a substrate such as a glass substrate or a silicon substrate by a method such as a spin coating method, a roll coating method, a slit-and-spin method, a die coating method or a bar coating method, Mu] m, preferably 0.5 to 5 [mu] m. Subsequently, if necessary, the resultant is subjected to reduced-pressure drying in a decompression chamber under a drying condition usually at 23 to 150 DEG C for 1 to 60 minutes, preferably at 60 to 120 DEG C for 1 to 10 minutes, A prebaking treatment is performed to form a film. Next, by a general photolithography method, radiation (for example, an electron beam or an ultraviolet ray can be applied and ultraviolet ray is preferable) is irradiated through a predetermined mask pattern, and an aqueous solution of a surfactant, an aqueous alkaline solution or a mixture of a surfactant and an alkaline agent Develop with an aqueous solution. Examples of the developing method include a dip method, a spray method, a shower method, a puddle method, and an ultrasonic developing method. Any of these methods may be used. After the unexposed portion is removed by rinsing with water and rinsed with water, post-baking treatment is performed under the conditions of usually 130 to 300 DEG C for 1 to 120 minutes, preferably 150 to 250 DEG C for 1 to 30 minutes, To obtain a colored cured film of the invention.

In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether and the like can be used as the surfactant. As the alkali agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide and the like can be used. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. The development is usually carried out at a treatment condition of 10 to 50 DEG C for 30 to 600 seconds, preferably 20 to 40 DEG C for 30 to 120 seconds.

The colored cured film of the present invention is useful as a color filter suitable for a liquid crystal display device, an organic EL display, a solid-state image pickup device used for a digital camera or the like. The color filter of the present invention is a pixel made of the colored cured film of the present invention prepared as described above.

The cured product of the colored resin composition of the present invention can be used for a color filter of a patterned blue pixel suitable for a liquid crystal display, an organic EL display, or a solid-state image pickup device used for a digital camera or the like, Are also included in the present invention.

The liquid crystal display of the present invention is fabricated, for example, in a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, Further, in the organic EL display, a color filter is formed on one or both of the multilayer organic light emitting elements. The solid-state image pickup device is manufactured by, for example, forming a color filter layer of the present invention on a silicon wafer on which a transfer electrode and a photodiode are formed, and then laminating a microlens.

The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper. The color liquid crystal display element having the color filter of the present invention may be of a transmissive type or a reflective type and may have a suitable structure. For example, a color filter is formed on a substrate separate from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which a driving substrate and a color filter are formed faces each other with a liquid crystal layer interposed therebetween A substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (indium oxide doped with tin) electrode is formed, It is also possible to adopt a structure that is opposed. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and precise liquid crystal display element can be obtained.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Unless otherwise stated in the examples, parts represent parts by mass. The physical properties in Examples were measured by the following methods.

(1) Epoxy equivalent: Measured by the method described in JIS K7236: 2001.

(2) Hardness: Measured according to the method described in JIS K5600-5-4: 1999.

(3) Refractive index: Measured by the method described in JIS K7142: 1996.

Next, in the calculation of the liquid refractive index, a solution-diluted sample was prepared so that the obtained compound concentration was changed by three points, and the refractive index of the liquid was measured at three points to calculate the liquid refractive index of the compound itself. The D line is 589 nm. The present invention is not limited at all by the following examples.

Synthesis Example 1 Synthesis of epoxy resin (a)

In a flask equipped with a thermometer, a cooling tube and a stirrer, 256 g of phenol compound N-phenylphenolphthalein (PPPBP manufactured by SABIC, purity: 99% or more), 842 g of epichlorohydrin and 180 g of methanol were added while purging with nitrogen gas, (Water bath) was heated to 75 占 폚. 21 g of flaky sodium hydroxide was added in portions over 90 minutes at the time when the internal temperature exceeded 65 캜, and the reaction was further carried out at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed twice with 300 g of water to remove salts and the like, and the reaction mixture was heated under reduced pressure (-70 ° C, -0.08 MPa to -0.09 MPa) and stirred for 3 hours. Excess epichlorohydrin And the like were distilled off. 600 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. 26 g of 30% by mass aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral. After washing with water, methyl isobutyl ketone or the like was distilled off under reduced pressure by a rotary evaporator to obtain 305 g of the intended epoxy resin (a). The obtained epoxy resin (a) had an epoxy equivalent of 266 g / eq., A softening point of 89 占 폚, an ICI melt viscosity of 0.42 Pa 占 퐏 (150 占 폚) and a solid at room temperature.

Example 1-1 Synthesis of Epoxycarboxylate Compound (A-1)

76.8 g of toluene as a diluting solvent, 135.6 g (0.6 eq.) Of the epoxy resin (a) obtained in Synthesis Example 1, and 2,6-di (tert-butyldimethoxysilane) as a heat polymerization inhibitor were placed in a 1 L flask equipped with a stirrer and a reflux tube, 0.53 g of -tert-butyl-p-cresol, 43.3 g (0.6 eq.) of acrylic acid as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, and 0.53 g of triphenylphosphine as a reaction catalyst, Hour, and the acid value was measured to be 1.7 mg KOH / g. Thus, the reaction was terminated. By this process, a resin solution of 70 mass% was obtained.

Subsequently, 250 g of toluene was added to this solution, and the mixture was washed three times with 100 g of water. The organic layer was concentrated under reduced pressure to obtain 161.0 g of the following pale yellow resin (A-1).

The physical properties of the compound (A-1) of the present invention are shown below.

Liquid refractive index (D line, 25 캜): 1.60

¹ H-NMR

3.58ppm = 2H, 3.96-4.42ppm = 10H, 5.58-5.60ppm = 2H, 6.04-6.05ppm = 2H, 6.26-6.27ppm = 2H, 6.86-6.88ppm = 4H, 7.12ppm = 1H, 7.15-7.19ppm = 6H, 7.42-7.43 ppm = 2H, 7.57-7.58 ppm = 1H, 7.80-7.81 ppm = 2H, 7.91 ppm = 1H

Example 1-2 Synthesis of epoxy carboxylate compound (A-2)

80.2 g of toluene as a diluting solvent, 135.6 g (0.6 eq.) Of the epoxy resin (a) obtained in Synthetic Example 1, 2, 6-di -butyl-p-cresol, 51.6 g (0.6 eq.) of methacrylic acid as a monocarboxylic acid compound having an ethylenic unsaturated group in the molecule, and 0.56 g of triphenylphosphine as a reaction catalyst were placed, For 24 hours, and the acid value was 2.1 mg KOH / g. Thus, the reaction was terminated. By this process, a resin solution of 70 mass% was obtained.

Then, 250 g of toluene was added to this solution, and the mixture was washed three times with 100 g of water. The organic layer was concentrated under reduced pressure to obtain 168.5 g of the following pale yellow resin (A-2). The structure of the compound was confirmed by measuring ¹ H-NMR.

The physical properties of the compound (A-2) of the present invention are shown below.

Liquid refractive index (D line, 25 캜): 1.59

¹ H-NMR

2.01ppm = 6H, 3.58ppm = 2H, 3.96-4.42ppm = 10H, 6.39-6.40ppm = 2H, 6.47-6.48ppm = 2H, 6.86-6.88ppm = 4H, 7.12ppm = 1H, 7.15-7.19ppm = 7.42-7.43 ppm = 2H, 7.57-7.58 ppm = 1H, 7.80-7.81 ppm = 2H, 7.91 ppm = 1H

Examples 1-3 and 1-4 Synthesis of polycarboxylic acid compounds (B-1) and (B-2)

The amount of the tetrahydrophthalic anhydride as the polybasic acid anhydride (c) as shown in Table 1 was added to the epoxy carboxylate compound (A-1) obtained in Example 1-1 and the amount of the reaction solution was adjusted so that the solid content of the reaction solution became 65% Toluene was added. Thereafter, the reaction was carried out at 100 占 폚 for 10 hours to obtain a solution of the polycarboxylic acid compound (B-1) and a solution of the polycarboxylic acid compound (B-2). Subsequently, this solution was washed three times with 100 g of water, and the organic layer was concentrated under reduced pressure to obtain a light yellow resin-like polycarboxylic acid compound (B). The set acid value in Table 1 means the desired solid acid value of the polycarboxylic acid compound finally obtained. The polybasic acid anhydride (c), which is a calculation amount for achieving the set acid value, was used.

Comparative Synthesis Example 1 (Synthesis of Compound (H-1)) A comparison with Japanese Laid-Open Patent Publication No. 9-272707

170 g of o-phenylphenol (O-PP Sanko Co., Ltd.), 370 g of epichlorohydrin, and 74 g of methanol were added and dissolved in a flask equipped with a thermometer, a cooling tube and a stirrer while purging with nitrogen gas. Further, the mixture was heated to 70 占 폚, 41 g of flaky sodium hydroxide was added in portions over 90 minutes, and then further reacted at 70 占 폚 for 60 minutes. After completion of the reaction, the resulting product was washed twice with 200 g of water to remove salts and the like, followed by heating under reduced pressure (-70 ° C, -0.08 MPa to -0.09 MPa), stirring for 3 hours, and excess epichlorohydrin And the like were distilled off. To the residue, 450 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 캜. 10 g of a 10% by mass aqueous solution of sodium hydroxide was added under stirring, and the reaction was conducted for 1 hour, followed by washing with water until the washing water became neutral. After washing with water, methyl isobutyl ketone or the like was distilled off under reduced pressure by a rotary evaporator to obtain 217 g of the intended epoxy resin. The obtained epoxy resin had an epoxy equivalent of 233 g / eq. And was in a liquid state at room temperature.

139.8 g (0.6 eq.) Of the obtained epoxy resin, 0.55 g of 2,6-di-t-butyl-p-cresol as a thermal polymerization inhibitor, 43.3 g (0.6 eq.) Of acrylic acid as the monocarboxylic acid compound (b) having unsaturated groups and 0.55 g of triphenylphosphine as a reaction catalyst were placed and reacted at 98 DEG C for 30 hours. As a result, KOH / g, the reaction was terminated. By this step, 180 g of a transparent, pale yellow resin-like compound (H-1) was obtained.

The liquid refractive indexes of the compounds of Examples and Comparative Examples and the compounds (H-1), (I-1) and (I-2) The liquid refractive index was calculated by preparing a sample diluted with a solvent so that the concentration of the obtained compound was changed by three points, measuring the refractive index of the liquid at three points, and calculating the liquid refractive index of the compound itself. The results are shown in Table 2.

week)

Measuring device: Multi-wavelength Abbe refractometer DR-M2 Atago Co., Ltd.

Measured wavelength: 589 nm (D line)

(I-1) OPP-1: manufactured by Nippon Kayaku Co., Ltd. (terminal acrylate ester of ethylene oxide adduct of 2-phenylphenol

(I-2) OGSOL EA-200 (manufactured by Osaka Gas Chemical Co., Ltd. (terminal acrylate ester of ethylene oxide adduct of bisphenol fluorene)

Example 2, Comparative Example 2 Preparation of resin composition and film for test

(A-1, A-2, B-1 and B-2) synthesized in Example 1 and the compounds (H-1), (I-1) and The resin compositions (Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 and the compounding amount (g)) blended in the composition shown in Table 3 were subjected to a heat treatment using a bar coater (No. 20) (A-4300, manufactured by Toyobo Co., Ltd., thickness: 188 mu m). The polyester film coated with the resin composition was allowed to stand in a drying oven at 80 DEG C for 1 minute, and then a high-pressure mercury lamp of 120 W / cm was used in an air atmosphere. The laminated film was irradiated at a conveyance speed of 5 m / Ultraviolet rays were irradiated to obtain a film having a cured coating (10 to 15 mu m).

week)

* 1: PET-30: KAYARAD PET-30 (mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate), manufactured by Nippon Kayaku Co., Ltd. (B-5)

* 2: Irg.184 (Irgacure 184): manufactured by Chiba Specialty Chemicals (1-hydroxycyclohexyl phenyl ketone)

* 3: MEK: methyl ethyl ketone

Test Example

The evaluation results of the following items are shown in Table 4 with respect to the film obtained in Example 2 or Comparative Example 2.

(Pencil hardness)

According to JIS K 5400, the pencil hardness of the coated film was measured using a pencil scratch. That is, a pencil was scratched about 5 mm on a polyester film having a cured coating film to be measured at an angle of 45 degrees with a load of 1 kg applied from above, and a state of scratching was confirmed. The measurement is performed five times, and the number of times of no sucking is counted.

Rating 5/5: No scratches in 5 times in 5 times

     0/5: All 5 scratches

(Scratch resistance)

A load of 200 g / cm < 2 > was applied on a steel wool # 0000 to make 10 reciprocations, and the state of the scratches was visually judged.

Evaluation 5: No occurrence of scratches was observed at all

Evaluation 4: Occurrence of 1 to 5 scratches was observed

Evaluation 3: Occurrence of 6 to 50 scratches was observed

Evaluation 2: Occurrence of 51 to 100 scratches was observed

Evaluation 1: Peeling of the film was observed

(Adhesion)

In accordance with JIS K 5400, 11 gaps of longitudinal and transverse angles were formed on the surface of the film at intervals of 1 mm to form 100 grid scales. After the cellophane tape was brought into close contact with the surface of the cellophane tape, the number of grid eyes remaining without being peeled off at one time was displayed.

(curl)

The polyester film having the cured coating film to be measured was cut into 5 cm x 5 cm, left in a drying furnace at 80 deg. C for 1 hour, and then returned to room temperature. The height of each of the four sides levitated on a horizontal stand was measured, and the average value was defined as a measured value (unit: mm). At this time, the curl of the substrate itself was 0 mm.

(Exterior)

Cracks, whitening, and cloudiness of the surface were judged visually.

Evaluation ○: Good

     ?: Small crack occurred

     X: Significant cracks

The cured product of the resin composition of the present invention was superior in hardness, scratch resistance and adhesion as compared with Comparative Example 2, and had a curl height equal to or lower than that of Comparative Example 2. From this point of view, it can be seen that the resin composition of the present invention has a smaller hardening shrinkage than that of Comparative Example 2.

Example 3 Preparation and evaluation of an active energy ray-curable optical resist

20 g of the polycarboxylic acid compound (B-1) obtained in Example 1-3, 5 g of dipentaerythritol hexaacrylate, which is a radical reactive monomer as the reactive compound (C), 5 g of an ultraviolet reactive photopolymerization initiator, 184 were mixed and dissolved by heating to obtain an optical composition.

This was coated on a quartz plate with a hand applicator to a film thickness of 20 microns at the time of drying, and the solvent was dried in an electric oven at 80 DEG C for 30 minutes. After drying, the mask pattern was covered from the coating material and irradiated with an ultraviolet ray having an irradiation dose of 1000 mJ / cm 2 by an ultraviolet vertical exposure apparatus equipped with a high-pressure mercury lamp (manufactured by OAK) to obtain an optical material. Subsequently, a 1% by mass aqueous solution of sodium carbonate was sprayed, and the unexposed portion was dissolved and developed. As a result, a pattern can be formed, and the polycarboxylic acid compound (B) of the present invention has resist suitability.

Comparative Synthesis Example 2 (Synthesis of Compound (H-2)

In a 1 L flask equipped with a stirrer and a reflux condenser, 89.6 g of toluene as a diluting solvent and 9.6 g of 9,9-bis [4- (glycidyloxy) phenyl] -9H- fluorene (manufactured by Osaka Gas Chemical Co., (0.6 eq.) As a thermal polymerization inhibitor, 0.63 g of 2,6-di-tert-butyl-p-cresol as a monocarboxylic acid compound having an ethylenic unsaturated group in the molecule, 46.5 g (0.6 eq.) Of triphenylphosphine as a reaction catalyst, 0.63 g of triphenylphosphine as a reaction catalyst, and reacted at 98 DEG C for 24 hours. As a result of acid value measurement, the reaction was terminated because the acid value was 0.3 mgKOH / g. By this process, a resin solution of 70 mass% was obtained.

Then, 250 g of toluene was added to the solution, and the mixture was washed three times with 100 g of water. The organic layer was concentrated under reduced pressure to obtain 9,9-bis [4- [2- hydroxy- ) Propoxy] phenyl] -9H-fluorene (H-2). The liquid refractive index and ¹ H-NMR of (H-2) are as follows.

Liquid refractive index (D line, 25 캜): 1.61

¹ H-NMR

3.95 ppm = 2H, 4.16ppm = 2H, 4.20ppm = 2H, 4.41ppm = 2H, 4.69ppm = 2H, 5.77ppm = 2H, 5.83ppm = 2H, 6.12ppm = 2H, 6.41ppm = 2H, 6.85ppm = 7.18 ppm = 4H, 7.28 ppm = 2H, 7.38 ppm = 2H, 7.55 ppm = 2H, 7.90 ppm = 2H

Synthesis of colorant (D1)

A cyanine dye (D1) represented by the following formula (2) was synthesized according to Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2014-153441.

Synthesis of colorant (D2)

A danthene dye (D2) represented by the following formula (3) was synthesized according to Synthesis Example 2 of JP-A-2013-050707.

Examples 4 and 5, Comparative Examples 3 and 4 Formulation of resin composition and preparation of cured product

The resin compositions (Examples 4, 5 and Comparative Examples) in which the compound (A-1) of Example 1-1 and the compounds (H-2) and (I- Examples 3-1 to 3-3, 4-1 to 4-3 (compounding amount (g)) were applied to the respective glass substrates and prebaked at 80 占 폚 for 10 minutes. Subsequently, the obtained coating film was exposed through a mask having a pattern, and the exposed portion was cured. Thereafter, the resultant was developed with an aqueous alkali solution containing a surfactant, rinsed with water, and cured by heating at 230 占 폚 for 30 minutes. As a result, an evaluation substrate having a colored pattern was obtained.

week)

DPHA: KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co.,

Colorant (D1): Cyanine dye

Colorant (D2): Zanthene dye

Binder resin (E-1): PSY-C1 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

NMP: N-methylpyrrolidone

Irg. 369 (Irgacure 369): manufactured by Chiba Specialty Chemicals (1-hydroxycyclohexyl phenyl ketone)

As a result of evaluating developability, resolution and adhesiveness to a substrate using the substrate for evaluation, the obtained pattern had a resolution of 5 탆 square in line and space, and peeling of the residue, Not confirmed. Therefore, the colored resin composition of the present invention is suitable for a color filter application requiring a high resolution for a solid-state image pickup device.

Test Example

The evaluation results of the following items are shown in Table 6 for the cured products obtained in Examples 4 and 5 and Comparative Examples 3 and 4.

(Heat resistance: color difference after post baking)

The spectral transmittance of the evaluation substrate was measured before and after the post-baking treatment for 30 minutes at 230 占 폚, and the color difference? Eab was calculated and evaluated. The smaller the color difference, the better.

(Solvent resistance: color difference before and after NMP immersion)

The evaluation substrate subjected to the post-baking treatment at 230 占 폚 for 30 minutes was immersed in N-methylpyrrolidone at 25 占 폚 for 15 minutes to measure the spectral transmittance before and after the immersion, and the color difference? Eab was calculated and evaluated.

Compared with the cured products using the cyanine dyes (Example 4 and Comparative Examples 3-1 to 3-3), the cured products of the present invention are superior in heat resistance to those of Comparative Examples, to be. Further, when the cured product using the xanthene dye (Example 5 and Comparative Example 4-1) is compared, the cured product of the present invention is equivalent in heat resistance. Among the cured products using a zanthene dye, it was found that the epoxy carboxylate compound used was inferior in heat resistance and solvent resistance to those of Example 5 in Comparative Examples 4-2 to 4-3 having the same aromatic ring as (A-1) .

The compound (A) of the present invention can be used in various fields as a photosensitive material and a color filter material having high heat resistance, high refractive index, excellent heat resistance and solvent resistance, and transparency, which are cured with active energy rays.

Claims (11)

An epoxy carboxylate compound (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having an ethylenically unsaturated group and a carboxyl group in a molecule:

(In the general formula (1), R ₁ is each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a represents the number of the substituent R ₁ , Or 2). The method according to claim 1,
An epoxy carboxylate compound (A) wherein, in the general formula (1), R ₁ is a hydrogen atom. A polycarboxylic acid compound (B) obtained by reacting the epoxy carboxylate compound (A) according to claim 1 with a polybasic acid anhydride (c). An epoxy carboxylate compound (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having an ethylenically unsaturated group and a carboxyl group in a molecule,

(In the general formula (1), R ₁ is each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a represents the number of the substituent R ₁ , Or 2), or
, And a polycarboxylic acid compound (B) obtained by reacting the epoxy carboxylate compound (A) with a polybasic acid anhydride (c). 5. The method of claim 4,
, And a reactive compound (C) other than the epoxy carboxylate compound (A) and the polycarboxylic acid compound (B). 6. The method of claim 5,
When the reactive compound (C) is a (poly) ester (meth) acrylate (C-1), a urethane (meth) acrylate (C-2), an epoxy (Meth) acrylate (C-4), alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) (C-8), a maleimide group-containing compound (C-8), a (meth) acrylamide compound (C-9) and an unsaturated polyester Or more. 6. The method of claim 5,
When the reactive compound (C) is a urethane (meth) acrylate (C-2), an alkyl (meth) acrylate or an alkylene -6). ≪ / RTI > A resin composition comprising the epoxy carboxylate compound (A), the colorant (D), and the binder resin (E) according to claim 1. A cured product of the resin composition according to any one of claims 4 to 8. A color filter having the cured product according to claim 9. A display element having the color filter according to claim 10.