TW201607966A - Epoxy (meth) acrylate compound, resin composition containing the same and its cured product - Google Patents

Abstract

An objective of the present invention is to provide a compound which is excellent in transparency and has a high refractive index, a resin composition which contains the compound and shows little shrinkage at curing, and a cured product having high scratch resistance, high adhesion and sufficient hardness. The present invention provides a compound (A) which is obtained by reacting a (meth)acrylic acid with an epoxy resin, that is obtained by reacting a phenol compound synthesized from a phenolphthalein derivative and an aminobenzene derivative with epichlorohydrin; and further provides a polycarboxylic acid compound (B) that is obtained by reacting the compound (A) with a polybasic acid anhydride (c); a resin composition which contains the compound (A) or the compound (B); and a resin composition which contains the compound (A), a colorant (C) and a binder resin (E).

Description

Epoxy (meth) acrylate compound and resin composition containing the same and cured product thereof

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

In recent years, photosensitive materials which are hardened by active energy rays, have high heat resistance and high refractive index, and have transparency are being continuously developed. In addition, a photosensitive material is often added to a monomer or a filler which imparts high heat resistance and high refractive index, and also provides adhesion to a substrate, hardness of a cured product, solubility to an alkali, and the like. additive. However, since it is difficult to express the characteristics of an organic material because the addition of these additives causes a decrease in refractive index or the like, it is necessary to increase the heat resistance and refractive index of the resin itself.

Patent Document 1 discloses the use of a reactant of o-phenylphenol glycidyl ether and (meth)acrylic acid as an optical material. However, the compound obtained in this way is a monofunctional (meth) acrylate having a hardened substance. Low hardness/heat resistance. Further, the liquid phase refractive index is about 1.58.

Patent Document 2 discloses a terminal acrylate compound using an ethylene oxide adduct of 2-phenylphenol as a transmissive screen material. However, this compound is a monofunctional (meth) acrylate having a low hardness/heat resistance of a cured product. Further, the liquid phase refractive index is about 1.57.

Patent Document 3 discloses the use of a resin composition comprising an amine ester compound derived from phenylphenol as an optical lens sheet material.

Patent Document 4 discloses the use of a resin composition comprising an amine ester compound derived from phenylphenol and a (meth) acrylate having an anthracene 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 an anthracene skeleton as an optical lens sheet material, but it has a close adhesion to a substrate due to its hard skeleton. The topic of sexuality and toughness. Further, there is no description of a pattern formed by an alkali developer depending on the adhesion to the carboxylic acid or the developability.

Patent Document 6 describes an epoxy resin having a 2-hydrocarbyl-3,3-bis(4-hydrocarbylaryl)benzylammonium amine skeleton, and is disclosed for use in an adhesive, a coating material, a coating agent, and the like. Patent Document 7 describes a resin composition containing the epoxy resin, a carboxylic acid, and/or a cationic polymerization catalyst, and discloses use for a glass substitute material, an adhesive, a coating material, a coating agent, and the like. Patent Document 8 also discloses an epoxy resin having a 2-hydrocarbyl-3,3-bis(4-hydrocarbylaryl)benzylideneamine skeleton.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-272707

[Patent Document 2] Japanese Patent Laid-Open No. Hei 5-065318

[Patent Document 3] International Publication 2008/136262A1

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-265346

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-094987

[Patent Document 6] GB1158606A

[Patent Document 7] International Publication 2013/183735A1

[Patent Document 8] International Publication 2013/183736A1

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

In order to solve the above problems, the inventors of the present invention have intensively studied and found that a compound having an unsaturated group having a specific structure and a resin composition containing the compound solve the above problems, and have completed the present invention.

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

(In the formula (1), R _{1 is} independently and is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and a represents a substituent R ₁ The number is 1 or 2).

Further, the present invention relates to the aforementioned epoxy carboxylate compound (A), wherein the compound (1) wherein R 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.

Further, the present invention relates to a polyvalent carboxylic acid compound (B) obtained by further reacting the above-mentioned epoxy carboxylate compound (A) with a polybasic acid anhydride (c).

Further, the present invention relates to a resin composition containing the above-described epoxy carboxylate compound (A) or polycarboxylic acid compound (B).

Further, in the present invention, the resin composition further contains the reactive compound (C) other than the epoxy carboxylic acid ester compound (A) and the polyvalent carboxylic acid compound (B).

Further, the present invention relates to the aforementioned resin composition, wherein the above reactive compound (C) is selected from the group consisting of (poly)ester (meth)acrylate (C-1) and amine ester (meth)acrylate (C- 2) Epoxy (meth) acrylate (C-3), (poly) ether (meth) acrylate (C-4), alkyl (meth) acrylate or alkyl (meth) acrylate ( C-5), (meth) acrylate (C-6) having an aromatic ring, having an alicyclic structure (meth) acrylate (C-7), a compound containing a maleimine group (C-8), a (meth) acrylamide compound (C-9), and an unsaturated polyester (C- 10) One or more compounds in the group.

Further, the present invention relates to the aforementioned resin composition, wherein the above reactive compound (C) is selected from the group consisting of an amine ester (meth) acrylate (C-2), an alkyl (meth) acrylate or (meth) acrylic acid. One or more compounds of the alkyl ester (C-5) and the (meth) acrylate (C-6) having an aromatic ring.

Further, the present invention relates to the aforementioned resin composition in which the refractive index (D line, 25 ° C) is from 1.52 to 1.72.

Further, the present invention relates to a resin composition comprising the above epoxy carboxylic acid ester compound (A), a colorant (D), and a binder resin (E).

Furthermore, the present invention relates to the resin composition, wherein the colorant (D) is selected from the group consisting of a xanthene dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, One or more kinds of azo dyes.

Furthermore, the present invention relates to the resin composition described above, wherein the binder resin (E) is a copolymer of a carboxyl group-containing unsaturated monomer and an unsaturated carboxylic acid ester.

Further, the present invention relates to a cured product of the aforementioned resin composition.

Further, the present invention relates to a color filter having the foregoing hardened material.

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

The epoxy carboxylic acid ester compound (A) of the present invention (for the epoxy resin (a) represented by the above formula (1) and having ethylene in the molecule a resin composition obtained by reacting an unsaturated group with a compound (b) of a carboxyl group, or a polycarboxylic acid compound (B) (for further reacting an epoxy carboxylate compound (A) with a polybasic acid anhydride (c) The cured product of the resin composition is excellent not only in the balance of heat resistance and moisture resistance but also in transparency and high refractive index. In addition, the cured material is a material excellent in mechanical properties such as toughness, heat resistance, and solvent resistance, and is particularly a material for forming a film which is excellent in adhesion to a substrate and scratch resistance. The resin composition of the present invention can be developed because it is water-soluble due to the alkalinity of the polycarboxylic acid, and is therefore suitable as a material for an optical resist. For example, optical applications such as a hard coat layer for a display device, a thin film, and an optical waveguide such as a liquid crystal display, such as a lens, a liquid crystal display, and the like, are suitable for a color filter and a display element having a color filter.

The resin composition of the present invention contains the above formula (1) (in the formula (1), R _{1 is} independently, and is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 to 6. Any one of alkoxy groups, a represents the number of substituents R ₁ , an epoxy resin (a) represented by 1 or 2), and a compound having an ethylenically unsaturated group and a carboxyl group in the molecule (b) The epoxy carboxylic acid ester compound (A) obtained by the reaction or the polyvalent carboxylic acid compound (B) obtained by further reacting the epoxy carboxylic acid ester compound (A) with the polybasic acid anhydride (c).

R ₁ in the formula (1) is appropriately selected depending on the use to be used. 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 are mentioned. Among these, from the viewpoint of obtaining materials, etc., it is preferable that the compound in which R _{1 is} a hydrogen atom.

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

The alkyl group having 1 to 6 carbon atoms in the present invention may be any of a straight chain, a branched chain, and a cyclic group. Preferred are methyl, ethyl or propyl.

The alkoxy group having 1 to 6 carbon atoms in the present invention may be any of a straight chain, a branched chain, and a cyclic group. Preferred is a methoxy group or an ethoxy group.

The halogen atom in the present invention may, for example, be a chlorine atom, a bromine atom or an iodine atom.

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

In the case of the present invention, it is particularly preferred that the epoxy resin (a) has an epoxy equivalent of 266 g/eq. This is because a large amount of ethylenically unsaturated bonds can be introduced into the epoxy carboxylic acid ester compound (A) and the polyvalent carboxylic acid compound (B), so that the obtained cured product is mechanically strong and becomes a tough resin.

The epoxy carboxylic acid ester compound (A) of the present invention is obtained by reacting the above epoxy resin (a) with a compound (b) having an ethylenically unsaturated group and a carboxyl group (epoxycarboxylic acid esterification step). The polyvalent carboxylic acid compound (B) of the present invention is obtained by further reacting an epoxy carboxylic acid ester compound (A) with a polybasic acid anhydride (c) (acid addition step).

By the aforementioned epoxy carboxylic acid esterification step, in epoxy resin The skeleton introduces an ethylenically unsaturated group of a reactive group of an active energy ray. Specifically, it is a reaction of an epoxy group with a carboxyl group. The compound (b) having both an ethylenically unsaturated group and a carboxyl group may, for example, be (meth)acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a compound having both an unsaturated group and a hydroxyl group. A compound obtained by reacting with a saturated or unsaturated dibasic acid or the like.

In the above-mentioned compound obtained by reacting a compound having an unsaturated group and a hydroxyl group with a saturated or unsaturated dibasic acid, for example, a (meth) acrylate derivative having one hydroxyl group in one molecule and A half ester obtained by a molar reaction of a saturated or unsaturated dibasic acid anhydride. For example, a hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate, and maleic anhydride, succinic anhydride, phthalic anhydride, The partial hydrogenation of phthalic anhydride is a compound obtained by reacting a saturated or unsaturated dibasic acid such as a total hydride, a trimellitic anhydride or a pyromellitic anhydride.

Among the above compounds, in view of the stability of the reaction between the epoxy resin (a) and the compound (b), the compound (b) is preferably a monocarboxylic acid. When a monocarboxylic acid and a polyvalent carboxylic acid are used in combination, the molar ratio of the molar amount of the monocarboxylic acid to the molar amount of the polycarboxylic acid is preferably 15 or more. As the compound (b), (meth)acrylic acid or cinnamic acid is preferred as the point of sensitivity to the active energy ray in the case of the resin composition.

The ratio of addition of the epoxy resin (a) to the compound (b) in this reaction is appropriately changed depending on the use. That is, when all of the epoxy groups are esterified with a carboxylic acid, since the unreacted epoxy group is not present, the epoxy carboxylate compound (A) has high storage stability. At this point, the hardening reaction system becomes only using the imported double The reactivity caused by the bond.

In the epoxy carboxylic acid esterification step in which the epoxy group is not left, the ratio of the addition of the epoxy resin (a) to the compound (b) is preferably 1 equivalent to the epoxy group of the epoxy resin (a). The carboxyl group of the compound (b) is from 0.90 to 1.20 equivalents. In this range, since the unreacted epoxy group remains or the unreacted epoxy group is small, it 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 in this range, the epoxy group remaining in the compound (a) is small, and the stability of the resin is improved.

On the other hand, the amount of the compound (b) to be added is reduced to leave an unreacted epoxy group, whereby the reaction caused by the introduced unsaturated bond can be reacted with the residual epoxy group (for example, A polymerization reaction by a photocationic catalyst, a thermal polymerization reaction, or the like) is used in combination for curing. At this time, the adhesion to the metal material or the like is improved, and the hardening shrinkage is reduced. However, attention should be paid to the preservation or manufacturing conditions of the epoxy carboxylate compound.

When the epoxy group is remaining, the carboxyl group of the compound (b) is added in an amount of 0.20 to 0.90 equivalent to 1 equivalent of the epoxy group of the epoxy resin (a). As long as it is within this range, the effect of composite hardening can be exerted. Further, in the case of remaining the epoxy group, it is necessary to pay attention to the gelation in the subsequent reaction and the stability with time of the epoxy carboxylate compound (A). Further, when the polycarboxylic acid compound (B) is used in the acid addition step described later, it is preferred that no epoxy group remains. In other words, when a large amount of the epoxy group remains, it reacts with the introduced carboxyl group, and the storage stability is particularly deteriorated.

The epoxy carboxylate esterification step is carried out without solvent or after dilution with a solvent. When a solvent is used, the solvent has no effect on the reaction, that is, Specially limited. The solvent may, for example, be an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene or tetramethylbenzene, or an aliphatic hydrocarbon solvent such as hexane, octane or decane, or a petroleum ether of a mixture of the above. Unleaded gasoline, solvent oil, ester solvent, ether solvent, ketone solvent, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate and diethylene glycol alone. Methyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl Monoether or monoalkylene glycol monoalkyl ether monoacetate; dialkyl glutarate, dialkyl succinate, A polyvalent alkyl carboxylate such as a dialkyl dicarboxylate.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether. A glycol ether such as a glycol ether, a triethylene glycol dimethyl ether or a triethylene glycol diethyl ether; a cyclic ether such as tetrahydrofuran or the like.

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

Further, as the solvent of the epoxy carboxylic acid esterification step, a reactive compound (C) or the like described later can be used. These solvents may be used singly or in combination. At this time, the resin composition of the present invention can be directly used.

In the epoxy carboxylic acid esterification step, a catalyst may also be used to promote the reaction. The amount of the catalyst used is about 0.1 to 10% by mass based on the total amount of the reactants. The catalyst may, for example, be triethylamine or benzyldi Methylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylsulfonium, methyltriphenylphosphonium, chromium octoate, octanoic acid An alkaline catalyst such as zirconium.

The reaction temperature of the epoxy carboxylic acid esterification step is from 60 to 150 °C. Moreover, the reaction time is preferably from 5 to 60 hours. For the thermal polymerization inhibitor of the epoxy carboxylic acid esterification step, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl bitter, diphenylamine, 3,5-di can be used. - TBT-hydroxytoluene and the like.

The epoxy carboxylic acid esterification step is appropriately sampled, and at the same time, the acid value of the sample (according to JIS K5601-2-1:1999) is 3 mg ‧ KOH / g or less, preferably 2 mg ‧ KOH / g or less The point is the end point.

Next, the acid addition step will be explained. The acid addition step is carried out by reacting a hydroxyl group produced by the epoxy carboxylic acid esterification step with a polybasic acid anhydride (c) to obtain a polyvalent carboxylic acid compound (B) having a carboxyl group introduced through an ester bond.

The polybasic acid anhydride (c) is not particularly limited as long as it is a compound having an acid anhydride structure in the molecule. For example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, which are excellent in alkaline aqueous developability, heat resistance, hydrolysis resistance, and the like, are preferable. 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

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

However, the plural used in the resin composition of the present invention When the carboxylic acid compound (B) is used as a base-developing type resist, the solid value (by JIS K5601-2-1:1999) of the finally obtained polycarboxylic acid compound (B) is added to 40 to 100 mg ‧ KOH The /g is preferably a polybasic acid anhydride (c) in a range of from 60 to 90 mg ‧ KOH / g. When the solid content acid value is smaller than this range, the developability of the alkaline aqueous solution of the resin composition is remarkably lowered, and in the worst case, development is impossible. In addition, when the solid content acid value exceeds the upper limit, the polybasic acid anhydride (c) is excessive in the reaction point, and the unreacted polybasic acid anhydride (c) remains in the composition, and the developability is too high to be formed. The situation of the pattern.

In the acid addition step, in order to promote the reaction, it is preferred to use a catalyst. The amount of the catalyst used is preferably from about 0.1 to 10% by mass based on the total amount of the reactants. The catalyst may, for example, be triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, or the like. Phenylhydrazine, methyltriphenylphosphonium, chromium octoate, zirconium octoate, and the like.

The reaction temperature of the acid addition step is from 60 to 150 °C. Moreover, the reaction time is preferably from 5 to 60 hours.

The acid addition step is carried out without solvent or by dilution with a solvent. When a solvent is used, the solvent is not particularly limited as long as it does not affect the reaction. Further, when the carboxylic acid esterification step in the previous step is carried out using a solvent, if it is a solvent which does not affect the acid addition step, it may be supplied to the acid addition step without removing the solvent.

The solvent may be the same solvent as the carboxylic acid esterification step.

For other solvents in the acid addition step, the reaction described later can be used. Compound (C) and the like. These solvents may be used singly or in combination. At this time, the resin composition of the present invention can be directly used. The thermal polymerization inhibitor of the acid addition step may be the same as the epoxycarboxylic acid esterification step described above. In the acid addition step, sampling can be appropriately performed, and the point at which the acid value of the reactant is in the range of plus or minus 10% of the acid value set for the intended use is used as the end point.

As described above, 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 compounds (C) other than the compound (A) or (B) as needed.

The reactive compound (C) in the present invention means a compound which can be reacted by an active energy ray. Specific examples thereof include (poly)ester (meth)acrylate (C-1), amine ester (meth)acrylate (C-2), and epoxy (meth)acrylate (C-3), ( Poly)ether (meth) acrylate (C-4), alkyl (meth) acrylate, alkyl (meth) acrylate (C-5), (meth) acrylate with aromatic ring (C- 6) a (meth) acrylate (C-7) having an alicyclic structure, a compound (C-8) containing a maleidino group, a (meth) acrylamide compound (C-9), and Unsaturated polyester (C-10), etc., but is not limited thereto.

The (poly)ester (meth)acrylate (C-1) may be used in combination with the resin composition of the present invention, and examples thereof include caprolactone-modified (2-)ethyl (meth)acrylate, ethylene oxide, and / or propylene oxide modified decanoic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified (meth) acrylate tetrahydrofurfuryl ester, etc. Ester (meth) acrylates; hydroxytrimethyl acetate neopentyl glycol di(meth) acrylate, caprolactone modification Di(poly)ester (meth) acrylates such as hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate and epichlorohydrin modified decanoic acid di(meth)acrylate; Hydroxymethylpropane or glycerol 1 molar addition of 1 mol or more of ε-caprolactone, γ-butyrolactone, δ-valerolactone or the like, resulting in a single, two or three triol (Meth) acrylate.

Further, a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone or δ-valerolactone which is added to 1 molar or more of neopentyl alcohol or di-trimethylolpropane 1 mole is exemplified. And mono-, di-, tri- or tetra (meth) acrylate of triol, ε-caprolactone, γ-butyrolactone, δ- at 1 molar above dipentaerythritol a mono-(meth) acrylate or a polyhydric alcohol of a triol or a poly(meth) acrylate triol, a tetraol, a pentaol or a hexaol, such as a lactone compound such as valerolactone (Meth) acrylate.

Further examples include: (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butanediol, 3-methyl-1,5-pentanediol, hexanediol And other diol components with maleic acid, fumaric acid, succinic acid, adipic acid, citric acid, isophthalic acid, hexahydrophthalic acid, tetrahydrofurfuric acid, dimer acid, azelaic acid, sebacic acid, 5 a polybasic acid such as sodium sulfonate isophthalic acid; and a (meth) acrylate of a polyester polyol having a reaction with an acid anhydride of the foregoing; comprising the diol component and a polybasic acid and an acid anhydride of the foregoing and ε-hexan a polyfunctional (poly) ester (meth) acrylate such as a (meth) acrylate of a cyclic lactone-modified polyester diol such as a lactone, γ-butyrolactone or δ-valerolactone, However, it is not limited to this.

The amine ester (meth) acrylate (C-2) which can be used in combination with the resin composition of the present invention is a hydroxy compound (C-2-methyl) having at least one (meth) acryloxy group and an isocyanate compound ( C-2-B) Base) The general name for acrylate.

Specific examples of the hydroxy compound (C-2-methyl) having at least one (meth) acryloxy group include, for example, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. , 2-hydroxybutyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol Various (meth) acrylate compounds having a hydroxyl group such as mono(meth)acrylate, pentaerythritol tri(meth)acrylate, or 2-hydroxy-3-phenoxypropyl (meth)acrylate; a ring-opening reactant of a hydroxy (meth) acrylate compound and ε-caprolactone, and the like.

Specific examples of the isocyanate compound (C-2-B) include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, and 2,4. -Aromatic diisocyanates such as methyl phenyl diisocyanate, 2,6-methylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene Diisocyanate of aliphatic or alicyclic structure such as bis-isocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and isocyanuric acid diisocyanate; one of isocyanate monomers a polyisocyanate such as a diuret or a diisomer of the above diisocyanate compound; a polyisocyanate obtained by esterifying the above isocyanate compound with the above polyol compound by an amine.

An epoxy (meth) acrylate (C-3) which can be used in combination with the resin composition of the present invention is an epoxy resin containing one or more epoxy groups. A general term for (meth) acrylate obtained by reacting (meth)acrylic acid. Specific examples of the epoxy resin as a raw material of the epoxy (meth) acrylate include phenyl condensed water such as hydroquinone diglycidyl ether, catechol diglycidyl ether, and resorcinol diglycidyl ether. Glycerol ether; bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-S epoxy resin, 2,2-bis(4-hydroxyphenyl)-1,1,1,3 a bisphenol epoxy compound such as an epoxy compound of 3,3-hexafluoropropane; a hydrogenated bisphenol-A epoxy resin, a hydrogenated bisphenol-F epoxy resin, a hydrogenated bisphenol-S epoxy resin, Hydrogenated bisphenol epoxy compound such as hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane; brominated bisphenol-A ring Halogenated bisphenol type epoxy compound such as oxygen resin, brominated bisphenol-F type epoxy resin; alicyclic diglycidyl ether compound such as cyclohexane dimethanol diglycidyl ether compound; 1,6-hexanediol II An aliphatic diglycidyl ether compound such as glycidyl ether, 1,4-butanediol diglycidyl ether or diethylene glycol diglycidyl ether; polysulfide type diglycidyl ether such as polythio diglycidyl ether Compound; phenol novolak type Oxygen resin, cresol novolak type epoxy resin, hydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol-type novolak type epoxy Resin, epoxy resin containing a naphthalene skeleton, heterocyclic epoxy resin, and the like.

(Poly)ether (meth)acrylate (C-4) which can be used together with the resin composition of the present invention, for example, butoxyethyl (meth)acrylate and butylene triethylene glycol (A) Acrylate, epichlorohydrin modified butyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, ethyl carbene Alcohol (meth) acrylate, phenoxyethyl (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, etc. Monofunctional (poly)ether (meth) acrylates.

For example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polytetramethylene glycol di(methyl) An alkylene glycol di(meth)acrylate such as acrylate; a copolymer of ethylene oxide and propylene oxide; a copolymer of propylene glycol and tetrahydrofuran; polyisoprene glycol, hydrogenated polyisoprene glycol, polybutylene a polyvalent hydroxy compound such as a hydrocarbon-based polyol such as a diene diol or a hydrogenated polybutadiene diol, and a polyfunctional (meth) acrylate derived from (meth)acrylic acid; in 1 mol of neopentyl glycol A di(meth) acrylate having a diol of 1 mol or more of a cyclic ether such as ethylene oxide, propylene oxide or butylene oxide is added.

The di(meth)acrylate of the bisphenol-based alkylene oxide modified product such as bisphenol A, bisphenol F or bisphenol S; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc. An alkylene oxide modified di(meth)acrylate of a hydrogenated bisphenol; an ethylene oxide, propylene oxide or butylene oxide having a molar content of 1 mole or more per 1 mole of trimethylolpropane or glycerin A mono-, di- or tri(meth)acrylate of a triol derived from a cyclic ether compound.

Further, it may further be a method of adding a triol of 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mol of neopentyltetraol or di-trimethylolpropane. Mono-, di-, tri- or tetra (meth) acrylate; a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide added to 1 mol of neopentyltetraol A polyfunctional (poly)ether (meth) acrylate such as a hexaol 3 or a hexafunctional (meth) acrylate.

(meth) propylene which can be used in combination with the resin composition of the present invention Examples of the acid alkyl ester or the alkyl (meth)acrylate (C-5) include octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, and (methyl). a monofunctional (meth) acrylate such as dodecyl acrylate.

For example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate A di(meth) acrylate of a hydrocarbon diol of 1,10-nonanediol di(meth) acrylate.

For example, mono(meth)acrylate, di(meth)acrylate or tri(meth)acrylate of trimethylolpropane (hereinafter, "poly" is collectively called difunctional, trifunctional, tetrafunctional, etc. Polyfunctional), mono (meth) acrylate or poly(meth) acrylate of glycerol, mono or poly (meth) acrylate of neopentyl alcohol, mono or poly (di-trimethylolpropane) Mono- or poly(meth)acrylates of polyhydric alcohols such as a triol, a tetraol or a hexaol, such as a mono- or poly(methyl) acrylate of m-) acrylate.

Further, a hydroxyl group-containing (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate may be mentioned.

The (meth) acrylate (C-6) having an aromatic ring which can be used in combination with the resin composition of the present invention may, for example, be phenyl (meth) acrylate, benzyl (meth) acrylate or 2-phenyl. a monofunctional (meth) acrylate such as a terminal acrylate adduct of a phenolic ethylene oxide adduct (for example, OPP-1 manufactured by Nippon Kayaku Co., Ltd.); bisphenol A di(meth)acrylic acid; Ester, bisphenol F A di(meth)acrylate such as di(meth)acrylate or the like is not limited thereto.

The (meth) acrylate (C-7) having an alicyclic structure which can be used in combination with the resin composition of the present invention may, for example, be cyclohexyl (meth)acrylate or cyclopentyl (meth)acrylate. Monofunctional (meth) acrylates having an alicyclic structure such as isodecyl methacrylate or dicyclopentenyl (meth) acrylate; hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F (meth) acrylate; polycyclic (meth) acrylate having a cyclic structure such as tricyclodecane dimethylol di(meth) acrylate; tetradecyl (meth) acrylate is equal to the structure The alicyclic (meth) acrylate having an oxygen atom or the like is not limited thereto.

Further, in the case of a compound having a (meth) acrylonitrile group which can be used in combination with the resin composition of the present invention, in addition to the above compounds, for example, (meth)acrylic acid polymer and (meth)acrylic acid can also be used. Poly(meth)acrylic acid polymer (meth) acrylate such as a reaction of glycidyl ester or a reaction product of a glycidyl (meth)acrylate polymer with (meth)acrylic acid; dimethyl (meth)acrylate a (meth) acrylate having an amine group such as an aminoethyl ester; a trimeric isocyanato (meth) acrylate such as a (meth) propylene oxyethyl tripolyisocyanate; having a polyoxyalkylene skeleton (Meth) acrylate; polybutadiene (meth) acrylate, melamine (meth) acrylate, and the like.

Further, the compound (C-8) containing a maleidino group which can be used in combination with the resin composition of the present invention may, for example, be N-n-butylmaleimide or N-hexylmaleimide. 2-maleimide ethyl-ethyl carbonate, 2-maleimide ethyl-propyl carbonate, N-ethyl-(2-maliania Monofunctional aliphatic maleimine such as amine ethyl)amine; alicyclic monofunctional maleimide such as N-cyclohexylmaleimine; N,N-hexamethylene Aliphatic bismaleimide such as bismaleimide, polypropylene glycol-bis(3-maleimidopropyl)ether, bis(2-maleimidoethyl)carbonate; , 4-dimaleimide cyclohexane, isophorone diamine ester bis (N-ethyl maleimide) and other alicyclic bimaleimide; maleic imine acetate and poly The esterification of tetramethylene glycol obtained by esterification of maleic imine compound, maleic imine hexanoic acid and neopentyl alcohol tetraethylene oxide adduct The (poly)ester (poly)maleimide compound obtained by esterifying a carboxylated maleimide derivative such as an amine compound with various (poly) alcohols is not limited thereto.

The (meth) acrylamide compound (C-9) which can be used in combination with the resin composition of the present invention may, for example, be monofunctional (such as propylene morpholine or N-isopropyl (meth) acrylamide) ( Methyl) acrylamide; polyfunctional (meth) acrylamide such as methylene bis(meth) acrylamide.

Examples of the unsaturated polyester (C-10) which can be used in combination with the resin composition of the present invention include fumaric acid esters such as dimethyl fumarate and diethyl fumarate; and maleic acid, fumaric acid and the like. An esterification reaction of a saturated carboxylic acid with a polyol.

The reactive compound (C) which can be used for the resin composition of the present invention is preferably (C-2), (C-5), and (C-6), and particularly preferably (C-5).

In the resin composition of the present invention containing the reactive compound (C), the ratio of use of the compound (A) or (B) of the present invention to the reactive compound (C) is (A) or (B): (C) = 5:95 to 95:5 (unit: mass%), preferably (A) or (B): (C) = 20:80 to 80:20 (unit: mass%).

The resin composition of the present invention is easily hardened by active energy rays. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, and particle beams such as α rays, β rays, and electron beams. In view of the application suitable for the present invention, the active energy ray is preferably ultraviolet light, laser light, visible light, or an electron beam.

The refractive index (D line, 25 ° C) of the resin composition of the present invention can be easily adjusted. A refractive index (D line, 25 ° C) in the range 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 hardened.

In order to make the resin composition of the present invention suitable for various uses, other components may be added to the resin composition at an upper limit of 90% by mass. Other components may be suitably used: a polymerization initiator, a solvent, a non-reactive compound, an inorganic filler, an organic filler, a decane coupling agent, an adhesion promoter, an antifoaming agent, a leveling agent, a plasticizer, an antioxidant, UV absorbers, flame retardants, dyes, etc. The other ingredients that can be used are exemplified below.

Examples of the radical photopolymerization initiator include benzoin 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, diethyl Acetophenone, such as oxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one Class; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-pentyl hydrazine and the like; 2,4-diethyl sulphide Thioxanthone such as ketone, 2-isopropylthioxanthone or 2-chlorothiazepin; 2,2-dimethoxy-2-phenylacetophenone, phenyl Acetals such as (α,α-dimethoxybenzyl) ketone; benzophenone, 4,4'-thiobis(2-methyl-1,3-benzenediol), 4,4' a benzophenone such as bismethylaminobenzophenone; 2,4,6-trimethylbenzylidenediphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) A conventional radical type photoreaction initiator such as a phosphine oxide such as a phenylphosphine oxide.

Further, an azo-based initiator such as azobisisobutyronitrile or a peroxide-based radical initiator which induces heat such as benzamidine peroxide may be used in combination. The initiator may be used singly or in combination of two or more.

The solvent may be the same solvent as the above-described carboxylic acid esterification step and the aforementioned acid addition step. These solvents may be used singly or in combination.

The non-reactive compound is a liquid or solid oligomer or resin which is low in reactivity or non-reactive, and examples thereof include an alkyl (meth)acrylate copolymer, an epoxy resin, and a liquid polybutadiene. , dicyclopentadiene derivative, saturated polyester oligomer, xylene resin, polyurethane polymer, ketone resin, diallyl phthalate resin (DAP resin), petroleum resin, rosin resin, The fluorine-based oligomer, the polyoxynoxy-based oligomer, and the like are not limited thereto.

Examples of the inorganic filler include cerium oxide, cerium oxide, calcium carbonate, calcium citrate, magnesium carbonate, magnesium oxide, titanium oxide, zirconium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, and aluminum hydroxide. , alumina, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon Wait. In the inorganic filler, a halogen group or an epoxy group may be added by adding a decane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, or the like. a functional group of a hydroxyl group or a thiol group.

Examples of the organic filler include benzoguanamine resin, polyoxyn epoxide resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene/acrylic acid copolymer, polystyrene, acrylic copolymer, polymethacrylic acid. Methyl ester resin, fluororesin, nylon 12, nylon 6/66, phenol resin, epoxy resin, amine ester resin, polyimide resin, and the like.

Examples of the decane coupling agent include a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane or γ-chloropropyltrimethoxydecane, and tetrakis(2,2-dipropoxymethyl-1-). Butyl) bis(di(tridecyl))phosphite titanate, bis(dioctylpyrophosphate) extended ethyl titanate, etc.; titanyloxydiisopropyl An aluminum coupling agent such as aluminum alkoxide; a zirconium coupling agent such as an acetonitrile acetone/zirconium complex; and the like.

A tackifier, an antifoaming agent, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, and a dye which can be used in the resin composition of the present invention can be used as long as it is a conventional one. The range of the curability and resin properties which impair the resin composition is not particularly limited.

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.

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

The coloring agent (D) of the present invention appropriately selects a color and a material depending on the use of a color filter or the like. Specifically, the coloring agent may be a pigment, a dye, or a natural coloring matter, and the above-mentioned coloring agents may be used singly or in combination of two or more. Among them, in order to obtain a pixel having high brightness, contrast, and color purity, it is preferably at least one selected from the group consisting of a pigment and a dye.

Preferred examples of the above organic pigment include a color pigment index (CI) named CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, and 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 pigment include carbon black, titanium black, and the like.

The pigment is also preferably a lake pigment. Specifically, a triarylmethane dye or a dibenzopyran dye is subjected to laking with a polypoly acid or a heteropoly acid (laking). )By. The triarylmethane-based lake pigment is disclosed, for example, in JP-A-2011-186043. The dibenzopyran-based lake pigment is disclosed, for example, in JP-A-2010-191304.

Further, the dye is preferably a dibenzopyran dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye or the like. More specifically, JP-A-2010-32999, JP-A-2010-254964, and JP-A-2011-138094 Japanese Laid-Open Patent Publication No. H10-123071, Japanese Laid-Open Patent Publication No. 2011-116803, JP-A-2011-117995, JP-A-2011-133844, and JP-A-2011-174987 Organic dyes.

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

In the present invention, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination of these methods. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. Further, the organic pigment can be used by refining the primary particles by a so-called salt milling treatment. For the method of the salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

When a pigment is used as the colorant in the present invention, a dispersing agent or a dispersing aid may be used in combination as needed. As the dispersing agent, for example, a suitable dispersing agent such as a cationic system, an anionic system or a nonionic system can be used, but a polymer dispersant is preferred. Specific examples thereof include an acrylic copolymer, a polyurethane, a polyester, a polyethyleneimine, and a polyallylamine.

These dispersants are commercially available. For example, examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (manufactured by BYK Co., Ltd.) and the like; and amine ester-based dispersants include Disperbyk-161 and Disperbyk. -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc.; Examples of the dispersant include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and the like, and examples of the polyester-based dispersant include Ajisper PB821, Ajisper PB822, Ajisper PB880, and Ajisper PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.).

Further, specific examples of the pigment derivative include a copper phthalocyanine, a diketopyrrolopyrrole, a sulfonic acid derivative of quinophthalone, and the like.

With respect to the content of the colorant (D), the colorant is usually from 0.01 to 70 parts by mass, more preferably from 0.5 to 50 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition of the present invention. It is more preferably in the range of 1.0 to 40 parts by mass.

The binder resin (E) in the present invention functions as a dispersing agent and a dispersing aid for the dispersion stability at the time of dispersion of the colorant (D). Further, when the colored resin composition is used in the photolithography method, the binder resin (E) is preferably an alkali developer used in the development treatment step in which the colorant (D) is soluble in the production of the color filter. In order to form a good fine pattern, the binder resin (E) is preferably provided with sufficient curing properties such as a photopolymerization initiator and a photopolymerizable monomer. In addition, the binder resin (E) is selected to have good compatibility with constituent materials such as a color material compound, a photopolymerization initiator, a photopolymerizable monomer, and a pigment dispersion liquid, and the colored resin composition does not precipitate or aggregate. By. When the colored resin composition is used in the inkjet method, since alkali solubility is not particularly required, it is only necessary to select a binder resin (E) which is excellent in compatibility with other constituent materials.

A binder resin (E) may be a conventional resin, preferably The ethylenically unsaturated monomer having one or more carboxyl groups or hydroxyl groups listed below or a copolymerizable copolymerizable aromatic hydrocarbon group or an aliphatic hydrocarbon group-containing ethylenically unsaturated monomer may be mentioned. Further, an epoxy acrylate resin having an epoxy group or a further acrylate may be used in the side chain or the terminal of the above. These monomers or the like may be used alone or in combination of two or more.

The carboxyl group-containing unsaturated monomer which is a raw material of the binder resin may be used, and examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids (anhydrides) such as acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; unsaturated polycarboxylic acids of more than 3 yuan ( Anhydrides, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate and 2-propenyloxyethyl- 2-hydroxyethyl decanoic acid and the like. These carboxyl group-containing ethylenically unsaturated monomers may be used singly or in combination of two or more kinds.

The hydroxyl group-containing unsaturated monomer which is a raw material of the binder resin can be used, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3. -hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 3-hydroxypentyl methacrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-(meth)acrylic acid 5- Hydroxy-3-methyl-pentyl ester, cyclohexane-1,4-dimethanol-mono(meth)acrylate, 2-(2-hydroxyethyloxy)ethyl (meth)acrylate, monomethyl Glyceryl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (methyl) A hydroxyl terminated polyalkylene glycol mono(meth)acrylate such as acrylate or poly(ethylene glycol-propylene glycol) monomethacrylate. These hydroxyl group-containing ethylenically unsaturated monomers may be used singly or in combination of two or more kinds.

Further, examples of the unsaturated monomer other than the above which can be used as a raw material of the binder resin include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and the like. An aromatic vinyl compound such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene or p-methoxystyrene; methyl (meth)acrylate, ethyl (meth)acrylate, (a) Base) n-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, (meth) acrylate Tributyl ester, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, p-isopropylphenoxyethylene glycol (meth)acrylate, 2-hydroxy-3 (meth)acrylate -phenoxypropyl ester, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate and phenoxyethyl (meth) acrylate are unsaturated Carboxylic esters; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, (methyl) propyl Acid thiomethyl ester, phenyl decyl methacrylate, cyano decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (methyl) Menthol acrylate, decyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl hydroxyalkyl (meth) acrylate, tricyclo(methyl) acrylate [5.2.1.0 ^2,6 ]癸-8-yl ester, tricyclo[methyl]acrylic acid [5.2.1.0 ^2,6 ]indole-4-methyl ester, cyclomethicone (meth)acrylate, 2-(methyl)propenyloxyethyl Alicyclic skeletons such as hexahydrononanoic acid and tributylcyclohexyl (meth)acrylate; polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and poly(ethylene glycol) - propylene glycol) monohydroxy acrylate-terminated polyalkylene glycol mono(meth) acrylates; methoxy polyethylene glycol monomethacrylate, lauryloxy polyethylene glycol mono (methyl) Acrylate, octyloxy polyethylene glycol, polypropylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, and allyloxy polyethylene Glycol-polypropylene glycol mono(methyl) propylene Alkyl-terminated polyalkylene glycol mono(meth)acrylates such as esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-methacrylic acid 2- Aminoalkyl esters of unsaturated carboxylic acids such as aminopropyl propyl ester, 3-aminopropyl acrylate and 3-aminopropyl methacrylate; glycidyl acrylate, glycidyl methacrylate, (methyl) Unsaturated carboxylic acid glycidyl esters such as 3,4-epoxybutyl acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidol Unsaturated ethers such as ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N- Phenylmaleimide, N-cyclohexylmaleimide, N-(meth)acrylonitrile, N-(2-hydroxyethyl)propenamide, N-(2-hydroxyl Ethyl) Unsaturated guanamine or unsaturated quinone imine such as acrylamide and maleimide; 1,3-butadiene, isoprene and chlorine equal aliphatic conjugated diene; and polystyrene , polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate and polysilicone are equal to the end of the polymer molecular chain with a mono propylene group or a single A macromonomer such as a acryl group. These unsaturated monomers may be used singly or in combination of two or more kinds.

When a binder resin (copolymer) is produced, a polymerization initiator is used. Specific examples of the polymerization initiator used in the synthesis of the copolymer include, for example, α,α'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile). , perbutyl octanoate, di-tert-butyl peroxide, benzamidine peroxide, methyl ethyl ketone peroxide, and the like. The polymerization initiator is used in a proportion of 0.01 to 25 parts by mass based on 100 parts by mass of all the monomers used in the synthesis of the copolymer. Further, in the case of synthesizing a copolymer, it is preferred to use an organic solvent, and to use a sufficient dissolving power for a monofunctional monomer, a polymerization initiator or the like to be used. The organic solvent used for the production of the binder resin may be the same as the organic solvent contained in the colored resin composition of the present invention to be described later.

The reaction temperature at the time of synthesizing the copolymer is preferably from 50 to 120 ° C, particularly preferably from 80 to 100 ° C. Further, the reaction time is preferably from 1 to 60 hours, more preferably from 3 to 20 hours. The preferred acid value of the copolymer is from 10 to 300 (mgKOH/g), preferably from 10 to 200 (mgKOH/g). When the acid value or the hydroxyl value is 10 or less, the developability is lowered. The weight average molecular weight (Mw) of the copolymer is preferably from 2,000 to 400,000, more preferably from 3,000 to 100,000. When the weight average molecular weight is 2,000 or less or 400,000 or more, sensitivity and developability are lowered. Further, the acid value in the present invention means a value measured according to the method of JIS K-2501, the hydroxyl value means a value measured according to the method of JIS K-1557, and the weight average molecular weight means a GPC (gel permeation layer). The measurement result of the analysis was calculated in terms of polystyrene.

Further, a polymer in which a side chain of the copolymer is further introduced with an unsaturated double bond can also be used as the binder resin. For example, the maleic anhydride moiety and the hydroxyethyl acrylate such as a copolymer of maleic anhydride and styrene, vinyl phenol, acrylic acid, acrylate, acrylamide, etc. copolymerizable with maleic anhydride are alcoholic. a hydroxy acrylate, a glycidyl methacrylate or the like having an epoxy group, and a half esterified compound; and a copolymer of an acrylate having an alcoholic hydroxyl group such as acrylic acid, acrylate or hydroxyethyl acrylate a compound in which a hydroxyl group reacts with acrylic acid or the like. Further, an amine ester resin, a polyamide, a polyimide resin, a polyester resin, a commercially available PSY-C1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) ACA-200M (manufactured by DAICEL Co., Ltd.), ORGA-3060 (Osaka) can also be used. Organic Chemicals), AX3-BNX02 (made by Nippon Shokubai), UXE-3024 (made by Nippon Kayaku Co., Ltd.), UTE-3000 (made by Nippon Kasei Co., Ltd.), ZGA-287H (made by Nippon Kasei Co., Ltd.), TCR-1338H (Japan) Chemicals), ZXR-1722H (manufactured by Nippon Kasei Co., Ltd.), ZFR-1401H (manufactured by Nippon Kasei Co., Ltd.), and ZCR-1642H (manufactured by Nippon Kayaku Co., Ltd.) are used as binder resins.

The binder resin (E) can be used singly or in combination of two or more kinds of the colored resin compositions of the present invention.

The binder resin (E) which can be used in the resin composition of the present invention is preferably a copolymer of a carboxyl group-containing unsaturated monomer and the above unsaturated carboxylic acid ester. The copolymer, for example, PSY-C1 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), is commercially available.

In terms of the content ratio of the binder resin (E) of the colored resin composition of the present invention, the total solid content of the colored resin composition is 100. The amount is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass. When the content of the binder resin (E) is less than 0.5 part by mass, the alkali developability is lowered, and problems such as contamination and residual film may occur in a region other than the portion where the pixel is formed.

In the colored resin composition for a color filter of the present invention, an organic solvent can be used in combination for the purpose of reducing the viscosity of the colored resin composition and improving the workability in coating the colored resin composition. As the organic solvent, it is preferred to use a binder resin, a photopolymerization initiator or the like which is a constituent component of the colored resin composition, and to have a sufficient dissolving power, a monofunctional monomer used for synthesizing the binder resin, and a polymerization initiation. Agents and the like also have sufficient solvency. Further, it is also preferred to use a dispersion stability even when a pigment dispersion is prepared.

Specific examples of the organic solvent containing the colored resin composition of the present invention include benzenes such as benzene, toluene and xylene; acesulfames such as methyl acesulfame, ethyl acesulfame, and butyl acesulfame ; cyanoic acid esters such as methyl cyproterone acetate, ethyl cyproterone acetate and butyl cyproterone acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acid esters and propylene glycol monobutyl ether acetate; methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethoxypropionic acid Propionates such as ethyl ester; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Acetate such as ester, ethyl acetate and butyl acetate; dimethyl ether, diethyl ether, tetrahydrofuran and Ethers such as alkane; 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, etc. However, it is not limited to this.

The organic solvent can be used singly or in combination of two or more kinds of the colored resin compositions of the present invention. The amount of the organic solvent used in the colored resin composition of the present invention is usually 10,000 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 further contain a photopolymerization initiator and/or a hardening accelerator. The photopolymerization initiator may contain a photopolymerization initiator, and is preferably one which is sufficiently sensitive to ultraviolet rays emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source, and may also be initiated by radically polymerizable photoradicals. Any one of a solvent, an ion curable photoacid generator, or a photobase generator. Further, in order to harden with less exposure energy, a polymerization accelerator component called a sensitizer may be used in combination. Specific examples of the photopolymerization initiator include benzil, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, and 3,3'-dimethyl Base 4-methoxybenzophenone, benzhydrazinobenzyl acid, ester of benzindenic acid, 4-benzylindolyl-4'-methyldiphenyl sulfide, benzyldimethyl Ketone, 2-butoxyethyl-4-methylaminobenzyl ester, chlorthiazinone, methyl thianonanone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl Thiopone, diethyl thiazinone, diisopropyl thioxanthone, dimethylaminomethyl benzyl ester, 1-(4-dodecylphenyl)-2-hydroxy- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)- 2-hydroxy-2-methylpropan-1-one, methyl benzalkonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2,4-bis(trichloromethyl)-6-(4-methoxybenzene Base)-1,3,5-all three , 2,4,6-gin (trichloromethyl)-1,3,5-all three , 2,4-bis(tribromomethyl)-6-(4'-methoxyphenyl)-1,3,5-all three , 2,4,6-parade (tribromomethyl)-1,3,5-all three , 2,4-bis(trichloromethyl)-6-(1,3-benzodioxol-5-yl)-1,3,5-all three , benzophenone, benzindenic acid, 1-(4-phenylthiophenyl)butane-1,2-dione-2-indole-O-benzylate, 1-(4-methyl Thiophenyl)butane-1,2-dione-2-indole-O-acetate, 1-(4-methylthiophenyl)butan-1-one oxime-O-acetic acid Ester, 4,4'-bis(diethylamino)benzophenone, isoamyl P-dimethylaminobenzylate, ethyl P-dimethylaminobenzylate, 2,2' - bis(O-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, diazonaphthoquinone-based initiator; and commercially available Kayacure DMBI, Kayacure BDMK , Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kasei Co., Ltd.), Darocur 1173, Darocur 1116 (all manufactured by Merck Japan), Irgacure 907 (manufactured by BASF Japan), Irgacure 369 (BASF) Japan made), Irgacure 379EG (manufactured by BASF Japan), Irgacure OXE-01 (manufactured by BASF Japan), Irgacure OXE-02 (manufactured by BASF Japan), Irgacure PAG103 (manufactured by BASF Japan), TME-III (Sanhe and CHEMICAL), biimidazole (black gold chemical system), STR-110, STR-1 (all manufactured by RESPE CHEMICAL), etc., but are not limited thereto.

In the coloring resin composition of the present invention, the photopolymerization initiators may be used singly or in combination of two or more kinds. The content of the photopolymerization initiator is usually 0.5 with respect to 100 parts by mass of the total solid content of the colored resin composition. It is 50 parts by mass, preferably 1 to 25 parts by mass.

The curing accelerator which may be contained in the coloring resin composition for a color filter of the present invention is a reaction catalyst for promoting ion hardening, and examples thereof include a N-containing heterocyclic compound such as an amine or an imidazole of the first to third grades, and an acid anhydride.

Specific examples of the amine include triethylamine, triethanolamine, Kayahard A-A, Kayabond C-100, Kayabond C-200S, Kayabond C-300S, and the like.

Specific examples of the imidazole include: Curezol 2MZ-H, Curezol C11Z, Curezol C17Z, Curezol 1, 2DMZ, Curezol 2E4MZ, Curezol 2PZ, Curezol 2P4MZ, Curezol 1B2MZ, Curezol 1B2PZ, Curezol 2MZ-CN, Curezol C11Z-CN, Curezol 2E4MZ-CN, Curezol 2PZ-CN, Curezol C11Z-CNS, Curezol 2PZCNS-PW, Curezol 2MZ-A, Curezol C11Z-A, Curezol 2E4MZ-A, Curezol 2MA-OK, Curezol 2PZ-OK, Curezol 2PHZ-PW, Curezol 2P4MHZ-PW, Curezol TBZ, Curezol 2PZL-T, Curezol VT, Curezol SFZ, and the like.

Specific examples of the acid anhydride include maleic anhydride, succinic anhydride, decanoic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and Kayahard MCD of Nippon Chemical Co., Ltd., and the like. Among these acid anhydrides, the hardening accelerator is preferably an imidazole, and more preferably Curezol 1B2PZ, Curezol 2PZ, Curezol 1B2MZ, and Curezol 2E4MZ in terms of reactivity.

The content of the hardening 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. The content of the hardening accelerator is less than 0.01 parts by mass In the case of a reduction in hardenability, when it exceeds 50 parts by mass, there is a problem that the stability of storage is deteriorated.

When the solubility of the resin component of the coloring agent (D) is low, it can be dispersed by using a dispersing agent, a dispersing aid, or the like, and a dispersing agent or the like can be used as a pigment dispersing agent and a resin system which have good adsorptivity to a dye. Dispersing agents, surfactants, and the like. As a dye-based dispersant, a method of mixing a sulfonate of a dye or a metal salt thereof with a dye, a method of mixing a substituted aminomethyl derivative, and the like are generally known. The resin-based dispersant is also a non-polar non-ionic one, and generally has a polymer resin having a good acid adsorption property such as an acid value and an amine valence, and examples thereof include an acrylic resin, a polyurethane resin, a polycarboxylic acid, and a poly Amidoxime resin, polyester resin, and the like. For example, ED211 (manufactured by Nanmoto Chemical Co., Ltd.), Ajisper PB821 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Solsperse 71000 (manufactured by Avecia), Disperbyk-2001 (manufactured by BYK Japan), and the like are exemplified.

Further, when an acid dye or a basic dye is used, it is known to modify the dye to an amine salt dye by reacting the dye with an organic amine compound (for example, n-propylamine or ethylhexylpropionamide) or to The sulfonic acid group is reacted with the same organic amine compound to be modified into a sulfonamide-based dye or the like to be soluble in an organic solvent, and is used in combination with an organic solvent. These amine-modified dyes may also be used in combination with the colored resin composition of the present invention. An amine-modified dye, in the colorant index, for example, solvent blue 2, 3, 4, 5, 6, 23, 35, 36, 37, 38, 43, 48, 58, 59, 67, 70 , 78, 98, 102, 104; basic blue 7; acid blue 80, 83, 90; purple dye solvent purple 8, 9; purple 4, 5, 14; alkaline purple 10 and so on.

The colored resin composition of the present invention can be produced by mixing and stirring a compound (A), a colorant (D), a binder resin (E), and any other additives by a dissolver, a homomixer, or the like. When the coloring agent (D) is a pigment or a dye having low solubility, the compound (A), the dispersion, and the binder are mixed by using a dispersing agent such as a paint shaker (Paint Shaker) to form a dispersion. The resin (E) was obtained to obtain a colored resin composition.

In the colored resin composition of the present invention, various additives such as a filler, a surfactant, a thermal polymerization inhibitor, a close adhesion promoter, an antioxidant, an ultraviolet absorber, a deagglomerating agent and the like may be further added as needed. Further, the colored resin composition of the present invention may be precisely filtered by a filter or the like in order to remove foreign matter or the like after the preparation.

The method for producing a coloring cured film for color filters (hereinafter also referred to as "coloring cured film") using the coloring resin composition of the present invention mainly includes a photolithography method and an inkjet method, and the former uses a photopolymerization initiator. A photosensitive colored resin composition having excellent developability, 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 by an inkjet method or the like, a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The thermal polymerization initiator is an azo compound or an organic peroxide, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethyl). Valeronitrile, 2,2'-azobis(2-methylbutyronitrile), di-tert-butyl peroxide, dibenzyl hydrazine peroxide, cumene peroxy neodecanoate, and the like.

Further, when a thermal polymerization initiator is used in combination, a photopolymerization initiator and The total of the thermal polymerization initiators may be used in an amount within the range of the content of the above photopolymerization initiator.

Next, a method of preparing a colored cured film from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is subjected to a spin coating method, a roll coating method, a slit and spin coating method, a die coating method, a bar coating method, or the like to have a film thickness of 0.1 to 20 μm, preferably 0.5. It is applied to a substrate such as a glass substrate or a tantalum substrate to a thickness of 5 μm. Then, depending on the required pressure in the pressure-reducing tank, drying under reduced pressure at a temperature of usually 23 to 150 ° C, 1 to 60 minutes, preferably 60 to 120 ° C, 1 to 10 minutes, and then using a hot plate or A dust-free oven or the like is pre-baked to form a film. Next, radiation is generally irradiated through a predetermined mask pattern by photolithography (for example, electron beam and ultraviolet light, preferably ultraviolet light), and an aqueous surfactant solution, an alkaline aqueous solution, or a surfactant and a base are used. The mixed aqueous solution of the agent is developed. Examples of the development method include a dipping method, a spray method, a shower method, a puddle method, and an ultrasonic development method, and these methods may be arbitrarily combined. The unirradiated portion is removed by development, and after being rinsed with water, it is usually subjected to post-baking treatment at 130 to 300 ° C for 1 to 120 minutes, preferably at 150 to 250 ° C for 1 to 30 minutes. The invention is a colored hardening film.

Among the above, polyoxyethylene ethyl ether, polyoxyalkylene alkyl ether or the like can be used as the surfactant. Further, as the alkali agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like can be used. In the present invention, it is preferred to use an aqueous solution containing both an alkali agent and a surfactant. The development is usually carried out under the treatment conditions of 10 to 50 ° C, 30 to 600 seconds, preferably 20 to 40 ° C, and 30 to 120 seconds.

The colored cured film of the present invention can be used as a color filter suitable for a liquid crystal display device, an organic EL display, or a solid-state imaging device used for a digital camera or the like. The color filter of the present invention comprises a pixel of the colored cured film of the present invention prepared in the above manner.

The cured product of the colored resin composition of the present invention can be used in a color filter of a patterned blue pixel suitable for a liquid crystal display device, an organic EL display, or a solid-state imaging device used for a digital camera or the like. The present invention also includes those equipped with the color filter and the like.

The liquid crystal display device of the present invention is, for example, 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, a polarizing film, and the like are laminated. Further, the organic EL display is fabricated by forming a color filter on either or both sides of the multilayer organic light-emitting element. The solid-state imaging element is produced by, for example, providing a color filter layer of the present invention on a wafer provided with a transfer electrode and a photodiode, and laminating the microlens.

The display element of the present invention is provided with 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 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 may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate for driving the substrate and a substrate on which the color filter is formed may be opposed to each other via a liquid crystal layer. The substrate on which the color filter is further formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed and the substrate on which the ITO (tin-doped indium oxide) electrode is formed may be opposed to each other via the liquid crystal layer. structure. The latter structure can particularly improve the aperture ratio, and has the advantage of a so-called bright and high-definition liquid crystal display element.

(Example)

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited to the examples. Further, in the examples, unless otherwise specified, the parts represent parts by mass. Further, each physical property value in the examples was measured by the following method.

(1) Epoxy equivalent: Measured according to 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 according to the method described in JIS K7142:1996.

Then, the following liquid phase refractive index was calculated by diluting with a solvent at a concentration of 3 points to prepare a sample, and measuring the liquid phase refractive index at three points to calculate the liquid phase refractive index of the compound itself. Moreover, the D line is 589 nm. Further, the present invention is not limited by the following examples.

Synthesis Example 1 Synthesis of Epoxy Resin (a)

Nitrogen gas purge was applied to a flask equipped with a thermometer, a cooling tube, and a stirrer, and phenol compound N-phenylphenolphthalein (PPPBP made by SABIC, purity 99% or more) 256 g, epichlorohydrin 842 g, methanol was added. 180 g, the water bath was heated to 75 °C. When the internal temperature exceeded 65 ° C, 21 g of flake sodium hydroxide was added in portions over a period of 90 minutes, and then the reaction was carried out at 70 ° C for 1 hour. After completion of the reaction, the mixture was washed twice with 300 g of water, and the resulting salt or the like was removed, and then heated under reduced pressure (to 70 ° C, -0.08 MPa). The mixture was stirred to -0.09 MPa, and excess epichlorohydrin or the like was distilled off at 3 hours. 600 g of dissolved methyl isobutyl ketone was added to the residue, and the temperature was raised to 70 °C. 26 g of a 30% by mass aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water was neutral. The water-washed solution was subjected to distillation of methyl isobutyl ketone or the like under reduced pressure by a rotary evaporator to obtain 305 g of the desired epoxy resin. The obtained epoxy resin had an epoxy equivalent of 266 g/eq., a softening point of 89 ° C, an ICI melt viscosity of 0.42 Pa s (150 ° C), and a solid at normal temperature.

Example 1-1 Synthesis of epoxy carboxylic acid ester compound (A-1)

76.8 g of toluene as a dilution solvent, 135.6 g (0.6 eq.) of the epoxy resin obtained in Synthesis Example 1, and 2,6-di-the first as a thermal polymerization inhibitor were added to a 1 L flask equipped with a stirring device and a reflux tube. Tributyl-p-cresol 0.53 g, 43.3 g (0.6 eq.) of acrylic acid as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, and 0.33 g of triphenylphosphine as a reaction catalyst, at 98 The reaction was carried out at ° C for 24 hours, and the acid value was determined to be 1.7 mg ‧ KOH / g, and the reaction was completed. 70% by mass of the resin solution was obtained by the above procedure.

Then, 250 g of toluene was added to the solution, and the mixture was washed three times with 100 g of water, and the organic layer was concentrated under reduced pressure to give 161.0 g of the compound (A-1) as pale yellow resin.

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

Liquid phase refractive index (D line, 25 ° C) 1.60

¹ H-NMR

3.58ppm=2H, 3.96-4.42ppm=10H, 5.58-5.60ppm=2H, 6.04-6.6.05ppm=2H, 6.26-6.27ppm=2H, 6.86-6.88ppm=4H, 7.12ppm=1H, 7.15-7.19ppm =6H, 7.42-7.43ppm=2H, 7.57-7.58ppm=1H, 7.80-7.81ppm=2H, 7.91ppm=1H

Example 1-2 Synthesis of epoxy carboxylic acid ester compound (A-2)

In a 1 L flask equipped with a stirring device and a reflux tube, 80.2 g of toluene as a diluent solvent, 135.6 g (0.6 eq.) of an epoxy resin obtained in Synthesis Example 1, and 2,6-di- as a thermal polymerization inhibitor were added. 0.56 g of a third butyl-p-cresol, 51.6 g (0.6 eq.) of methacrylic acid as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, and triphenylphosphine as a reaction catalyst 0.56 g After reacting at 98 ° C for 24 hours, the acid value was determined to be 2.1 mg ‧ KOH / g, and the reaction was completed. 70% by mass of the resin solution was obtained by the above procedure.

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

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

Liquid phase refractive index (D line, 25 ° C) 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=6H, 7.42-7.43ppm=2H, 7.57-7.58ppm=1H, 7.80-7.81ppm=2H, 7.91ppm=1H

Synthesis of polycarboxylic acid compound (B)

The epoxy carboxylic acid ester compound (A-1) obtained in Example 1-1 was added with tetrahydrophthalic anhydride as the polybasic acid anhydride (c) in an amount described in Table 1, and the solid content of the reaction liquid was 65% by mass. In this way, toluene as a solvent is added. Thereafter, the mixture was reacted at 100 ° C for 10 hours to obtain a polycarboxylic acid compound (B-1) solution and a polycarboxylic acid compound (B-2) solution. Then, this solution was washed three times with 100 g of water, and the organic layer was concentrated under reduced pressure to give a polycarboxylic acid compound (B) as a pale yellow resin. The acid value set in Table 1 means the desired solid acid value of the finally obtained polycarboxylic acid compound. The polybasic acid anhydride (c) is used in order to achieve the calculated amount of the acid value.

Comparative Synthesis Example 1 (Synthesis of Compound (H-1)) and Japanese Patent Publication No. 9-272707

A flask equipped with a thermometer, a cooling tube, and a stirrer was purged with nitrogen, and 170 g of o-phenylphenol (manufactured by O-PP Sanko Co., Ltd.), 370 g of epichlorohydrin, and 74 g of methanol were added and dissolved. Further, the mixture was heated to 70 ° C, and 41 g of flake sodium hydroxide was added in portions over a period of 90 minutes, and then reacted at 70 ° C for 60 minutes. After completion of the reaction, the mixture was washed twice with 200 g of water to remove the formed salt and the like, and then stirred under heating and reduced pressure (to 70 ° C, -0.08 MPa to -0.09 MPa), and the excess was distilled off at 3 hours. Epichlorohydrin and the like. 450 g of dissolved methyl isobutyl ketone was added to the residue, and the temperature was raised to 70 °C. 10 g of a 10% by mass aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water was neutral. The water-washed solution was subjected to distillation under reduced pressure of methyl isobutyl ketone or the like by a rotary evaporator to obtain 217 g of the desired epoxy resin. The obtained epoxy resin had an epoxy equivalent of 233 g/eq. and was liquid at normal temperature.

In a 1 L flask equipped with a stirring device and a reflux tube, 139.8 g (0.6 eq.) of the obtained epoxy resin and 2,6-di-t-butyl-p-cresol 0.55 g as a thermal polymerization inhibitor were added. 43.3 g (0.6 eq.) of acrylic acid as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and 0.55 g of triphenylphosphine as a reaction catalyst, which were reacted at 98 ° C for 30 hours. The acid value was 2.4 mg ‧ KOH / g, and the reaction was completed. By the above procedure, 180 g of a compound (H-1) as a transparent pale yellow resin was obtained.

The liquid phase refractive indices of the compounds of the examples and the comparative examples and the compounds (H-1), (I-1), and (I-2) are shown in Table 2. Further, the calculation of the liquid phase refractive index was carried out by diluting with a solvent at a concentration of three points to prepare a sample, and the liquid phase refractive index was measured at three points to calculate the liquid phase refractive index of the compound itself. The results are shown in Table 2.

Note)

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

Measurement wavelength: 589 nm (D line)

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

(I-2) OGSOL EA-200: manufactured by Osaka Gas Chemicals Co., Ltd. (terminal acrylate of ethylene oxide adduct of bisphenolphthalein)

Example 2 and Comparative Example 2 Preparation of a resin composition and preparation of a test film

The compound (A-1, A-2, B-1, B-2) synthesized in Example 1 and the compound (H-1) obtained in Comparative Example 1 and (I-1) and (I-2) were The resin compositions (Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3; blending amount (g)) prepared by the composition shown in Table 3 were coated with a bar coater (No. 20). Yu Yi then processed the polyester film (manufactured by Toyobo Co., Ltd.: A-4300, film thickness: 188 μm). The polyester film coated with the resin composition was allowed to stand in a drying oven at 80 ° C for 1 minute, and then irradiated with a high-pressure mercury lamp of 120 W/cm in an air atmosphere at a transport speed of 5 m/min from a lamp height of 10 cm. Ultraviolet rays were obtained to obtain a film having a hardened film (10 to 15 μm).

Note)

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

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

*3: MEK: methyl ethyl ketone

Test case

For the film obtained in Example 2 or Comparative Example 2, the evaluation results of the following items are shown in Table 4.

(pencil hardness)

The pencil hardness of the coated film was measured by pencil scratching in accordance with JIS K 5400. That is, on the polyester film having the hardened film measured, the pencil was applied with a load of 1 kg from the top at an angle of 45 degrees, and scratched by about 5 mm, and the damage was confirmed. The measurement was performed 5 times, and the number of times without damage was calculated.

Evaluation 5/5: 5 out of 5 times without damage

0/5: 5 times have damage

(scratch resistance)

A load of 200 g/cm ² was applied to the steel wool #0000, and the steel wool was reciprocated 10 times to visually judge the damage condition.

Assessment 5: No damage was observed at all

Assessment 4: 1 to 5 lesions were observed to occur

Assessment 3: 6 to 50 lesions were observed to occur

Assessment 2: 51 to 100 lesions were observed to occur

Evaluation 1: Observed peeling of the film

(close adhesion)

According to JIS K 5400, 11 vertical and horizontal cuts were cut at intervals of 1 mm on the surface of the film to make 100 checkerboards. Record the number of squares that remain without peeling off when the transparent tape is tightly bonded to the surface and the transparent tape is peeled off in one go.

(warping)

The polyester film having a hardened film to be measured was cut into 5 cm × 5 cm, and placed in a drying oven at 80 ° C for 1 hour, and then returned to room temperature. The heights of the four sides of the float were measured on a horizontal stage, and the average value was measured (unit: mm). At this time, the warpage of the substrate itself was 0 mm.

(Exterior)

The state of cracks, whitening, fogging, etc. of the surface is visually judged.

Evaluation ○: Good

△: a little crack is generated

×: significant cracks are produced

The cured product of the resin composition of the present invention was compared with Comparative Example 2, and was excellent in hardness, scratch resistance, and adhesion, and the warpage height was the same as that of Comparative Example 2 or Comparative Example 2 low. From this, it is understood that the curing shrinkage of the resin composition of the present invention is less than that of Comparative Example 2.

Example 3 Modulation and evaluation of active energy ray hardening type optical resist

20 g of the polycarboxylic acid compound (B-1) obtained in Example 1-3, 5 g of the radical-reactive monomer dipentaerythritol hexaacrylate as the reactive compound (C), and 1.5 g as an ultraviolet reaction The IRGACURE 184 of the photopolymerization initiator was mixed and dissolved by heating to obtain an optical composition.

The composition for optics was applied to a quartz plate by a hand coater so as to have a film thickness of 20 μm when dried, and the solvent was dried in an electric oven at 80 ° C for 30 minutes. After drying, the reticle pattern was covered from the upper side of the coated object, and ultraviolet ray was irradiated with an irradiation dose of 1000 mJ/cm ² by an ultraviolet vertical exposure apparatus (manufactured by ORC Co., Ltd.) equipped with a high-pressure mercury lamp to obtain an optical material. Then, 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, indicating that the polycarboxylic acid compound (B) of the present invention has resistivity.

Comparative Synthesis Example 2 (synthesis of compound (H-2))

To a 1 L flask equipped with a stirring device and a reflux tube, 89.6 g of toluene as a diluent solvent, 9,9-bis[4-(glycidoxy)phenyl]-9H-oxime (Osaka Gas Chemicals Co., Ltd.) was added. PG-100) 162.5 g (0.6 eq.), 0.63 g of 2,6-di-t-butyl-p-cresol as a thermal polymerization inhibitor, as a single having ethylenic unsaturation in the molecule 46.5 g (0.6 eq.) of the carboxylic acid compound and 0.63 g of triphenylphosphine as a reaction catalyst were reacted at 98 ° C for 24 hours, and the acid value was determined to be 0.3 mg ‧ KOH / g, and the reaction was completed. 70% by mass of the resin solution was obtained by the above procedure.

Then, 250 g of toluene was added to the solution, and the mixture was washed three times with 100 g of water, and the organic layer was concentrated under reduced pressure to give 9,9-bis[4-[2-hydroxy-3-(propyleneoxy) as a pale yellow resin. Propoxy]phenyl]-9H-indole (H-1) 189.0 g. The liquid phase refractive index of (H-1) and ¹ H-NMR were as follows.

Liquid phase refractive index (D line, 25 ° C): 1.61

¹ H-NMR

3.95ppm=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=4H, 7.18ppm=4H, 7.28ppm=2H, 7.38ppm=2H, 7.55ppm=2H, 7.90ppm=2H.

Synthesis of colorant (D1)

The cyanine dye (D1) represented by the following formula (2) was synthesized in accordance with Synthesis Example 1 of JP-A-2014-153441.

Synthesis of colorant (D2)

The dibenzopyran-based dye (D2) represented by the following formula (3) was synthesized in accordance with Synthesis Example 2 of JP-A-2013-050707.

Examples 4 and 5, Comparative Examples 3 and 4 Preparation of a resin composition and formation of a cured product

The compound (A-1) of Example 1-1 and the compound (H-2) obtained in Comparative Synthesis Example 2 and (I-2) a resin composition prepared according to the composition shown in Table 5 (Examples 4 and 5) And Comparative Examples 3-1 to 3-3, 4-1 to 4-3; the compounding amount (g) were respectively applied to a glass substrate, and prebaked at 80 ° C for 10 minutes. Then, the resulting coating film is exposed through a patterned mask to expose Partial hardening. Thereafter, development was carried out with an alkaline aqueous solution containing a surfactant, and after rinsing with water, the mixture was heat-cured at 230 ° C for 30 minutes. As a result, a substrate for evaluation having a colored pattern was obtained.

Note)

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

Colorant (D1): Cyanine dye

Colorant (D2): Dibenzopyran dye

Adhesive Resin (E-1): PSY-C1 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

NMP: N-methylpyrrolidone

Irg. 369 (IRGACURE 369): (1-hydroxycyclohexyl phenyl ketone) manufactured by Ciba Specialty Chemicals

Using the evaluation substrate, the developability, the resolution, and the adhesion to the substrate were evaluated. The obtained pattern had a resolution of 5 μm ² in line & pitch, and no residue or speckle peeling was observed. Therefore, the colored resin composition of the present invention is suitably used for a high-resolution color filter which requires a solid-state image sensor.

Test case

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 above-mentioned evaluation substrate was measured before and after the post-baking treatment at 230 ° C for 30 minutes, and the color difference (ΔEab) was calculated and evaluated. The smaller the color difference is, the more excellent it is.

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

The evaluation substrate which was post-baked at 230 ° C for 30 minutes was immersed in N-methylpyrrolidone at 25 ° C for 15 minutes, and the spectral transmittance before and after the immersion was measured, and the color difference (ΔEab) was calculated and evaluated.

The cured product of the cyanine dye (Example 4, Comparative Examples 3-1 to 3-3) was compared, and the cured product of the present invention was particularly excellent in heat resistance and solvent resistance as compared with the comparative example. Equivalent to the above. and Further, the cured product of the dibenzopyran-based dye (Example 5 and Comparative Example 4-1) was used, and the cured product of the present invention was equivalent to heat resistance. In the cured product of the dibenzopyran dye, the heat resistance was compared with respect to Comparative Examples 4-2 to 4-3 in which the epoxy carboxylate compound used had the same aromatic ring as (A-1). The solvent resistance was worse than that of Example 2.

(industrial availability)

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

Claims (12)

An epoxy carboxylic acid ester compound (A) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a compound (b) having an ethylenically unsaturated group and a carboxyl group in the molecule. The epoxy carboxylate compound (A); In the formula (1), R ₁ is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and a represents the number of substituents R ₁ and is 1 Or 2. The epoxy carboxylic acid ester compound (A) according to the first aspect of the invention, wherein R ₁ in the formula (1) is a hydrogen atom. A polyvalent carboxylic acid compound (B) obtained by further reacting the epoxy carboxylic acid ester compound (A) described in claim 1 with a polybasic acid anhydride (c). A resin composition comprising the epoxy carboxylic acid ester compound (A) according to claim 1 or 2. A resin composition comprising the polycarboxylic acid compound (B) according to item 3 of the patent application. The resin composition according to the fourth or fifth aspect of the invention is a reactive compound (C) other than the epoxy carboxylic acid ester compound (A) and the polyvalent carboxylic acid compound (B). The resin composition according to claim 6, wherein the reactive compound (C) is selected from the group consisting of (poly)ester (meth)acrylate (C-1) and amine ester (meth)acrylate ( C-2), epoxy (meth) acrylate (C-3), (poly) ether (meth) acrylate (C-4), alkyl (meth) acrylate or alkyl (meth) acrylate Ester (C-5), (meth) acrylate (C-6) having an aromatic ring, (meth) acrylate (C-7) having an alicyclic structure, and a compound containing a maleimine group ( C-8), one or more compounds selected from the group consisting of a (meth) acrylamide compound (C-9) and an unsaturated polyester (C-10). The resin composition according to claim 6, wherein the reactive compound (C) is selected from the group consisting of amine ester (meth) acrylate (C-2), alkyl (meth) acrylate or (methyl) One or more compounds selected from the group consisting of alkyl acrylate (C-5) and (meth) acrylate (C-6) having an aromatic ring. A resin composition comprising the epoxy resin (a) represented by the formula (1) and a compound (b) having an ethylenically unsaturated group and a carboxyl group in the molecule, as described in claim 1 The epoxy carboxylate compound (A), the colorant (D) and the binder resin (E) are obtained. A hardened material which is a cured product of the resin composition according to any one of claims 4 to 9. A color filter comprising the cured product of claim 10 of the patent application. A display element having the color filter described in claim 11 of the patent application.