JP6395505B2 - Epoxy (meth) acrylate compound, resin composition containing the same, and cured product thereof - Google Patents

Description

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

  In recent years, development of photosensitive materials that are cured with active energy rays, have high heat resistance and high refractive index, and have transparency has been promoted in various applications. In these applications, in addition to high heat resistance and high refractive index, adhesion to the substrate, hardness of the cured product, solubility in alkali, etc. are required. To meet these requirements, addition of monomers and fillers is required. Additives are often added. However, the addition of these additives makes it difficult to exhibit the characteristics of the organic material such as a decrease in the refractive index, so that it is necessary to improve the heat resistance and refractive index of the resin itself.

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

  Patent Document 2 discloses that a terminal acrylic ester of 2-phenylphenol ethylene oxide adduct is used as a transmission screen material. However, this compound is a monofunctional (meth) acrylate, and may have low hardness and heat resistance in the cured product, and the liquid refractive index is about 1.57.

  Patent Document 3 discloses that a resin composition containing a urethane compound obtained from phenylphenol is used as an optical lens sheet material.

  Patent Document 4 discloses that a resin composition containing a urethane compound obtained from phenylphenol and a (meth) acrylate having a fluorene skeleton is used as an optical lens sheet material.

  Although it is known in Patent Document 5 that a resin composition containing a (meth) acrylate having a phenylphenol skeleton and a fluorene skeleton is used as an optical lens sheet material, adhesion from the rigid skeleton to the substrate is known. There was a problem in property and toughness. Further, there is no description of imparting adhesion or developability by carboxylic acid modification or patterning with an alkali developer.

  Patent Document 6 describes an epoxy resin having a 2-hydrocarbyl-3,3-bis (4-hydroxyaryl) phthalimidine skeleton, and discloses application to adhesives, paints, coating agents, and the like. Patent Document 7 describes a resin composition containing the epoxy resin and a carboxylic acid and / or a cationic polymerization catalyst, and discloses uses for glass substitute materials, adhesives, paints, coating agents, and the like. Patent Document 8 also discloses an epoxy resin having a 2-hydrocarbyl-3,3-bis (4-hydroxyaryl) phthalimidine skeleton.

JP-A-9-272707 Japanese Patent Application Laid-Open No. 5-065318 International Publication 2008 / 136262A1 JP 2010-265346 A JP 2008-094987 A GB1158606A International Publication 2013 / 183735A1 International Publication 2013 / 183737A1

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

In order to solve the above-mentioned problems, the present inventors have found that an unsaturated group-containing compound having a specific structure and a resin composition containing the compound solve the above problems as a result of intensive studies. The present invention has been completed.
That is, the present invention provides an epoxy carboxylate compound obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule ( Regarding A).

（一般式（１）中、Ｒ_１はそれぞれ独立して、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基のいずれかから選ばれ、ａは置換基Ｒ_１の個数を表し、１又は２である。）

(In General Formula (1), each R ₁ is independently selected from any one 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 is a substituent R ₁ . Represents the number and is 1 or 2.)

Further, the epoxy carboxylate compound (1) wherein R ₁ in the general formula (1) is a hydrogen atom, and the compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule is (meth) acrylic acid or cinnamic acid ( Regarding A).
Furthermore, the present invention relates to a polycarboxylic acid compound (B) obtained by further reacting the epoxycarboxylate compound (A) with a polybasic acid anhydride (c).

Furthermore, it is related with the resin composition containing the said epoxy carboxylate compound (A) or a polycarboxylic acid compound (B).
Furthermore, it is related with the said resin composition containing reactive compounds (C) other than the said epoxycarboxylate compound (A) and a polycarboxylic acid compound (B).
Further, the reactive compound (C) is (poly) ester (meth) acrylate (C-1), urethane (meth) acrylate (C-2), epoxy (meth) acrylate (C-3), (poly) ether. (Meth) acrylate (C-4), alkyl (meth) acrylate or alkylene (meth) acrylate (C-5), (meth) acrylate (C-6) having an aromatic ring, (meth) acrylate having an alicyclic structure The compound which is at least one compound selected from the group consisting of (C-7), a maleimide group-containing compound (C-8), a (meth) acrylamide compound (C-9), and an unsaturated polyester (C-10). The present invention relates to a resin composition.
Further, the reactive compound (C) is urethane (meth) acrylate (C-2), alkyl (meth) acrylate or alkylene (meth) acrylate (C-5), and (meth) acrylate (C-) having an aromatic ring. It relates to the resin composition, which is one or more compounds selected from the group consisting of 6).
Furthermore, it is related with the said resin composition characterized by refractive index (D line, 25 degreeC) being 1.52-1.72.
Furthermore, it is related with the hardened | cured material of the said resin composition.

  The epoxy carboxylate compound (A) obtained by reacting the compound (b) having both an ethylenically unsaturated group and a carboxyl group in the molecule with the epoxy resin (a) represented by the general formula (1) of the present invention. ), Or a cured product of the resin composition containing the polycarboxylic acid compound (B) obtained by further reacting the polycarboxylate (c) with the epoxycarboxylate compound (A) is heat resistant. In addition to being excellent in balance between heat resistance and moisture resistance, it has transparency and a high refractive index. Further, the cured product is a material excellent in mechanical properties such as toughness, and in particular, is a film forming material excellent in adhesion to a substrate and scratch resistance. The resin composition of the present invention is suitable as a material used for so-called optical resists because it can be developed with polycarboxylic acid in an aqueous alkali solution. That is, for example, it is suitable for optical applications such as hard coatings for display devices such as lenses, optical disks, and liquid crystal displays, films, and photoconductive materials such as optical waveguides.

In the resin composition of the present invention, the general formula (1) (in the general formula (1), each R ₁ is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. And a compound having both an ethylenically unsaturated group and a carboxy group in the molecule (epoxy resin (a) represented by a represents the number of substituents R ₁ and is 1 or 2). an epoxycarboxylate compound (A) obtained by reacting b), or a polycarboxylic acid compound (B) obtained by reacting an epoxycarboxylate compound (A) with a polybasic acid anhydride (c) .

In the general formula (1), R ₁ should be appropriately selected according to the intended use. For example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and A halogen atom is mentioned. Of these, compounds in which R ₁ is all hydrogen atoms are most preferred from the standpoint of obtaining materials.

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

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

  In the present invention, the alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic. A methoxy group and an ethoxy group are preferable.

  In the present invention, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

The production method of the epoxy resin (a) represented by the general formula (1) is described in Patent Document 1, for example, and can be produced according to the method. Further, commercially available products (manufactured by Nippon Kayaku Co., Ltd. trade name: WHR-EP: wherein _{R 1} are all hydrogen atoms of the general formula (1), an epoxy equivalent of 266 g / eq) can also be used.

  Of the epoxy resins (a), those having an epoxy equivalent of less than 266 g / equivalent are particularly preferred. The reason is that more ethylenically unsaturated bonds can be introduced, so that the obtained cured product is imparted with mechanical strength and becomes a tougher resin.

  The epoxy carboxylate compound (A) of the present invention is obtained by reacting the epoxy resin (a) with a compound (b) having both an ethylenically unsaturated group and a carboxy group (epoxy carboxylate conversion step). The polycarboxylic acid compound (B) of the present invention is obtained by further reacting the polybasic acid anhydride (c) with the epoxycarboxylate compound (A) (acid addition step).

  The ethylenically unsaturated group which is the reactive group of the active energy ray is introduced into the skeleton of the epoxy resin by the epoxy carboxylation step. Specifically, it is a reaction of an epoxy group and a carboxy group. Examples of the compound (b) having both an ethylenically unsaturated group and a carboxy group are saturated with (meth) acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a compound having both an unsaturated group and a hydroxyl group. Or the compound etc. which reacted the unsaturated dibasic acid are mentioned.

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

  Among these, considering the stability of the reaction between the epoxy resin (a) and the compound (b), the compound (b) is preferably a monocarboxylic acid. When the monocarboxylic acid and the polycarboxylic acid are used in combination, the ratio of the molar amount of the monocarboxylic acid / the molar amount of the polycarboxylic acid is preferably 15 or more. The compound (b) is preferably (meth) acrylic acid or cinnamic acid from the viewpoint of sensitivity to active energy rays when a resin composition is used.

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

  In the epoxy carboxylation step in which no epoxy group remains, the charging ratio of the epoxy resin (a) and the compound (b) is such that the carboxy group of the compound (b) is equivalent to 1 equivalent of the epoxy group of the epoxy resin (a). 0.90 to 1.20 equivalents are preferred. If it is this range, since the unreacted epoxy group does not remain | survive or few, it does not gelatinize in an acid addition process, and the storage stability of resin is favorable. When the charged amount of the compound (b) is within this range, the epoxy group in which the compound (a) remains is small, and the stability of the resin is improved.

  On the other hand, by reducing the charged amount of the compound (b) and leaving an unreacted epoxy group, a reaction by the introduced unsaturated bond and a reaction by the remaining epoxy group (for example, a polymerization reaction or a thermal polymerization reaction by a photocation catalyst) ) Can be used in combination for curing. In this case, improvement in adhesion to a metal material or the like and reduction in curing shrinkage can be achieved. However, attention must be paid to the storage and production conditions of the epoxycarboxylate compound.

  When leaving an epoxy group, 0.20-0.90 equivalent of the carboxy group of a compound (b) is prepared with respect to 1 equivalent of epoxy groups of an epoxy resin (a). Within this range, the effect of composite curing is exhibited. Moreover, when leaving an epoxy group, it is necessary to pay attention to the gelation during the subsequent reaction and the temporal stability of the epoxycarboxylate compound (A). Furthermore, when using as a polycarboxylic acid compound (B) through the below-mentioned acid addition process, it is preferable not to leave an epoxy group. That is, when many epoxy groups remain, it reacts with the carboxy group to be introduced, and the storage stability is particularly deteriorated.

  In the epoxycarboxylation step, the reaction is carried out without solvent or diluted with a solvent. When a solvent is used, the solvent is not particularly limited as long as the reaction is not affected. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, petroleum ether, white gasoline, and mixtures thereof. Solvent naphtha, ester solvent, ether solvent, ketone solvent and the like can be mentioned.

  Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, and triethylene. Mono- or polyalkylene glycol monoalkyl ether monoacetates such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, dialkyl glutarate, dialkyl succinate, adipic acid Polycarboxylic acid alkyl esters such as dialkyl And the like.

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

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

  In addition, the reactive compound (C) described below can be used as a solvent in the epoxycarboxylate formation step. These solvents can be used alone or in combination. In this case, the resin composition of the present invention can be used as it is.

  A catalyst may be used during the epoxycarboxylation step to accelerate the reaction. The catalyst is used in an amount of about 0.1 to 10% by mass based on the total amount of the reactants. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. And basic catalysts.

  The reaction temperature in the epoxy carboxylate conversion step is 60 to 150 ° C. The reaction time is preferably 5 to 60 hours. For example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene can be used as a thermal polymerization inhibitor in the epoxy carboxylate formation step. .

  The epoxy carboxylate conversion step ends when 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, with appropriate sampling. And

  Next, the acid addition step will be described. The purpose of the acid addition step is to obtain a polycarboxylic acid compound (B) in which a carboxy group is introduced via an ester bond by reacting the polybasic acid anhydride (c) with the hydroxyl group produced in the epoxycarboxylate step. And

  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, 4- Methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride are preferred.

  An acid addition process can also be performed by adding a polybasic acid anhydride (c) to the reaction liquid of the said epoxy carboxylate-ized process. The amount of polybasic acid anhydride (c) added is appropriately changed according to the application.

  However, when the polycarboxylic acid compound (B) used in the resin composition of the present invention is used as an alkali development resist, the solid content acid value of the finally obtained polycarboxylic acid compound (B) (JIS K5601- 2-1: According to 1999) is charged with a calculated amount of polybasic acid anhydride (c) of 40 to 100 mg · KOH / g, preferably 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. When the solid content acid value exceeds this upper limit, the polybasic acid anhydride (c) becomes excessive with respect to the reaction point, and the unreacted polybasic acid anhydride (c) remains in the composition. In some cases, the developability becomes too high to allow patterning.

  It is preferable to use a catalyst to accelerate the reaction during the acid addition step. The amount of the catalyst used is preferably about 0.1 to 10% by mass based on the total amount of the reactants. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. Is mentioned.

  The reaction temperature in the acid addition step is 60 to 150 ° C. The reaction time is preferably 5 to 60 hours.

  In the acid addition step, the reaction is carried out without solvent or diluted with a solvent. When a solvent is used, the solvent is not particularly limited as long as the reaction is not affected. Moreover, when it manufactures using a solvent in the carboxylation process which is a previous process, you may use for an acid addition process, without removing a solvent, if it is a solvent which does not have influence on an acid addition process.

  Examples of the solvent include the same solvents as in the carboxylation step.

  In addition to this, as a solvent in the acid addition step, a reactive compound (C) described later can be used. These solvents can be used alone or in combination. In this case, the resin composition of the present invention can be used as it is. As the thermal polymerization inhibitor in the acid addition step, the same one as in the epoxy carboxylation step can be used. In the acid addition step, the end point is determined when the acid value of the reaction product is in the range of plus or minus 10% of the acid value set according to the intended use while sampling appropriately.

  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 necessary. Good.

  In the present invention, the reactive compound (C) refers to a compound that can react with active energy rays. Specific examples include (poly) ester (meth) acrylate (C-1), urethane (meth) acrylate (C-2), epoxy (meth) acrylate (C-3), (poly) ether (meth) acrylate (C -4), alkyl (meth) acrylate, alkylene (meth) acrylate (C-5), (meth) acrylate (C-6) having an aromatic ring, (meth) acrylate (C-7) having an alicyclic structure, maleimide Although group-containing compound (C-8), (meth) acrylamide compound (C-9), unsaturated polyester (C-10), etc. can be mentioned, it is not limited to these.

  Examples of the (poly) ester (meth) acrylate (C-1) that can be used in combination with the resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid ( Monofunctional (poly) ester (meth) acrylates such as (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) acrylate, Di (poly) ester (meth) acrylates such as caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate and epichlorohydrin-modified phthalic acid di (meth) acrylate; Chi trimethylolpropane or glycerol 1 mole to 1 mole or more ε- caprolactone, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as δ- valerolactone mono- include di- or tri (meth) acrylate.

  Furthermore, triol mono, di, tri or tetra (meta) obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane. ) Triol mono or poly (meth) acrylate obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of acrylate and dipentaerythritol Examples thereof include mono (meth) acrylate or poly (meth) acrylate of polyhydric alcohol such as all, pentaol or hexaol.

  Still further, diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol and maleic acid , Fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and their anhydrides (Meth) acrylate of a polyester polyol which is a reaction product with a product; a cyclic lactone-modified polyester diol composed of the diol component and a polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Multifunctional such as (meth) acrylate May be mentioned poly) ester (meth) acrylates such as, but not limited thereto.

  The urethane (meth) acrylate (C-2) that can be used in combination with the resin composition of the present invention comprises at least one (meth) acryloyloxy group-containing hydroxy compound (C-2-i) and an isocyanate compound (C-2-2). (B) A generic term for (meth) acrylates obtained by reaction with (b).

  Specific examples of the hydroxy compound (C-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy Ring-opening reaction product of (meth) acrylate compound having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and (meth) acrylate compound having the above hydroxyl group and ε-caprolactone Etc. can be mentioned.

  Specific examples of the isocyanate compound (C-2-ro) include, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate. Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of isocyanate monomer or the above diisocyanate compound It can be mentioned the with the isocyanate compound, polyisocyanate and the like obtained by the urethanization reaction of a polyol compound; the trimer polyisocyanates of the isocyanate and the like.

  The epoxy (meth) acrylate (C-3) that can be used in combination with the resin composition of the present invention is a (meth) acrylate obtained by reacting an epoxy resin containing one or more epoxy groups with (meth) acrylic acid. Is a general term. Specific examples of epoxy resins used as raw materials for epoxy (meth) acrylates include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy Resin, bisphenol-S type epoxy resin, bisphenol type epoxy compound such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound; hydrogenated bisphenol- A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane Epoxy Hydrogenated bisphenol type epoxy compounds such as compounds; Halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl such as cyclohexanedimethanol diglycidyl ether compounds Ether compounds; Aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether; Polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether; Phenol Novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadienephenol Epoxy resins, biphenol type epoxy resin, bisphenol -A novolac type epoxy resins, naphthalene skeleton-containing epoxy resin, a heterocyclic epoxy resin or the like.

  Examples of the (poly) ether (meth) acrylate (C-4) that can be used in combination with the resin composition of the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, and epichlorohydrin-modified butyl (meth). Monofunctional (such as acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate ( And poly) ether (meth) acrylates.

  Furthermore, alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; and ethylene oxide Polypropylene oxide copolymers, copolymers of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, polyhydric hydroxyl compounds such as hydrocarbon polyols such as hydrogenated polybutadiene glycol and the like (meth) Polyfunctional (meth) acrylates derived from acrylic acid; 1 mol or more of ethylene oxide, propylene oxide, butylene oxide per 1 mol of neopentyl glycol Diol di (meth) acrylate obtained by adding a cyclic ether such as de like.

  Further, alkylene oxides of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc .; di (meth) acrylates of modified alkylene oxides of bisphenols such as bisphenol A, bisphenol F and bisphenol S; Modified di (meth) acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of trimethylolpropane or glycerin ;

  Still further, a triol mono-, di-, tri- or tetra- (meth) acrylate obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of pentaerythritol or ditrimethylolpropane; Polyfunctional (poly) ether (meth) acrylates such as tri to hexafunctional (meth) acrylates of hexaol in which 1 mol or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide are added to 1 mol of erythritol Can be mentioned.

  Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (C-5) that can be used in combination with the resin composition of the present invention include octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, and dodecyl. And monofunctional (meth) acrylates such as (meth) acrylate.

  Furthermore, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Di (meth) of hydrocarbon diols of acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate Examples include acrylates.

  Furthermore, mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono of glycerin. Triols such as (meth) acrylate or poly (meth) acrylate, mono or poly (meth) acrylate of pentaerythritol, mono or poly (meth) acrylate of ditrimethylolpropane, mono or poly (meth) acrylate of dipentaerythritol, tetra Examples thereof include mono- or poly (meth) acrylates of polyhydric alcohols such as all and hexaol.

  Still further, there may be mentioned hydroxyl group-containing (meth) acrylic compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.

  Examples of the (meth) acrylate (C-6) having an aromatic ring that can be used in combination with the resin composition of the present invention include phenyl (meth) acrylate, benzyl (meth) acrylate, and an ethylene oxide adduct of 2-phenylphenol. Monofunctional (meth) acrylates such as terminal acrylic ester adducts (for example, OPP-1 manufactured by Nippon Kayaku Co., Ltd.); Di (meta) such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate ) Acrylates and the like can be mentioned, but not limited thereto.

  Examples of the (meth) acrylate (C-7) having an alicyclic structure that can be used in combination with the resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentenyl. Monofunctional (meth) acrylates having an alicyclic structure such as (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di (meth) Examples include polyfunctional (meth) acrylates having a cyclic structure such as acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate, etc. It is not limited to.

  Moreover, as a compound which has a (meth) acryloyl group which can be used together with the resin composition of the present invention, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or glycidyl other than the above-mentioned compounds Poly (meth) acrylic polymer (meth) acrylate such as a reaction product of (meth) acrylate polymer and (meth) acrylic acid; (meth) acrylate having amino group such as dimethylaminoethyl (meth) acrylate; Tris (meth) Isocyanur (meth) acrylates such as acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates, melamine (meth) acrylates, and the like can also be used.

  Examples of the maleimide group-containing compound (C-8) that can be used in combination with the resin composition of the present invention include Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, and 2-maleimidoethyl. -Monofunctional aliphatic maleimides such as propyl carbonate and N-ethyl- (2-maleimidoethyl) carbamate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene glycol- Aliphatic bismaleimides such as bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; Cycloaliphatic bismaleimides such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Maleimide acetic acid and polytet Obtained by esterification of carboxymaleimide derivatives such as maleimide compounds obtained by esterification with methylene glycol, maleimide compounds by esterification of maleimidocaproic acid with tetraethylene oxide adducts of pentaerythritol and various (poly) ols. (Poly) ester (poly) maleimide compounds and the like can be mentioned, but are not limited thereto.

  Examples of the (meth) acrylamide compound (C-9) that can be used in combination with the resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; methylenebis (meth) Examples include polyfunctional (meth) acrylamides such as acrylamide.

  Examples of the unsaturated polyester (C-10) that can be used in combination with the resin composition of the present invention include fumaric acid esters such as dimethyl maleate and diethyl maleate; polyunsaturated carboxylic acids such as maleic acid and fumaric acid And an esterification reaction product of polyhydric alcohol.

  As the reactive compound (C) that can be used in the resin composition of the present invention, (C-2), (C-5), and (C-6) are preferable, and (C-5) is particularly preferable.

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

  The resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, γ rays and laser rays, particle rays such as α rays, β rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  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 refers to a product obtained by irradiating and curing the active energy ray on the resin composition of the present invention.

  For the purpose of adapting the resin composition of the present invention to various uses, other components can be added to the resin composition up to 90% by mass. Other components include polymerization initiators, solvents, non-reactive compounds, inorganic fillers, organic fillers, silane coupling agents, tackifiers, antifoaming agents, leveling agents, plasticizers, antioxidants, UV absorption Agents, flame retardants, dyes and the like can be used as appropriate. Examples of other components that can be used are shown below.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Acetophenones such as phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acetals such as 2,2-dimethoxy-2-phenylacetophenone and phenyl (α, α-dimethoxybenzyl) ketone; Benzophenones such as benzophenone, 4,4′-thiobis (2-methyl-1,3-benzenediol), 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and other known radical type photoinitiators such as phosphine oxides.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

Examples of the solvent include the same solvents as those in the carboxylation step and the acid addition step. These solvents can be used alone or in combination.

  Non-reactive compounds are low-reactivity or non-reactive liquid or solid oligomers and resins, such as (meth) alkyl acrylate copolymers, epoxy resins, liquid polybutadiene, dicyclopentadiene derivatives, saturated Examples include, but are not limited to, polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine oligomers, and silicone oligomers.

  Examples of inorganic fillers include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, titanium oxide, zirconium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, Examples thereof include aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, and glass balloon. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen group, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group.

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

  Examples of the silane coupling agent include silane coupling agents such as γ-glycidoxypropyl tremethoxysilane and γ-chloropropyltrimethoxysilane, and tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl). ) Titanate coupling agents such as phosphite titanate and bis (dioctylpyrophosphate) ethylene titanate; Aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; Zirconium coupling agents such as acetylacetone / zirconium complex, etc. be able to.

  Any tackifier, antifoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant and dye that can be used in the resin composition of the present invention can be used. It can be used without particular limitation as long as the curability and resin properties are not impaired.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a mass part. In addition, each physical property value in an Example was measured with the following method.
(1) Epoxy equivalent: Measured by the method described in JIS K7236: 2001.
(2) Hardness: Measured by the method described in JIS K5600-5-4: 1999.
(3) Refractive index: Measured by the method described in JIS K7142: 1996.

  Next, in the following calculation of the liquid refractive index, a solvent-diluted sample was prepared so as to vary the obtained compound concentration by three points, the liquid refractive index was measured at three points, and the liquid refractive index of the compound itself was calculated. . The D line is 589 nm. In addition, this invention is not limited at all by the following examples.

Synthesis Example 1 Synthesis of Epoxy Resin (a) 256 g of N-phenylphenolphthalein (PPB made by SABIC, purity 99% or more) which is a phenol compound while purging a flask equipped with a thermometer, a cooler and a stirrer with a nitrogen gas purge , 842 g of epichlorohydrin and 180 g of methanol were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C., 21 g of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 300 g of water to remove the generated salt and the like, and then an excess amount was added in 3 hours with stirring under heating under reduced pressure (˜70 ° C., −0.08 MPa to −0.09 MPa). Epichlorohydrin and the like were distilled off. To the residue, 600 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 26 g of a 30% by mass aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water until the washing water became neutral. Methyl isobutyl ketone and the like were distilled off from the washed solution under reduced pressure using a rotary evaporator to obtain 305 g of the desired epoxy resin. The epoxy equivalent of the obtained epoxy resin is 266 g / eq. The softening point was 89 ° C., the ICI melt viscosity was 0.42 Pa · s (150 ° C.), and it was solid at room temperature.

Example 1-1 Synthesis of Epoxy Carboxylate Compound (A-1) In a 1 L flask equipped with a stirrer and a reflux tube, 76.8 g of toluene as a diluent solvent and 135. of the epoxy resin obtained in Synthesis Example 1 were used. 6 g (0.6 eq.), 0.53 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and acrylic acid as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule 43.3 g (0.6 eq.), 0.53 g of triphenylphosphine was charged as a reaction catalyst, reacted at 98 ° C. for 24 hours, and the acid value measured was 1.7 mg · KOH / g. Ended. By this step, a 70% by mass resin solution was obtained.
Next, 250 g of toluene was added to this solution, washed with 100 g of water three times, and the organic layer was concentrated under reduced pressure to obtain 161.0 g of the following pale yellow resinous compound (A-1).

The physical properties of the compound (A-1) of the present invention are shown below.
Liquid refractive index (D line, 25 ° C.) 1.60
¹ H-NMR
3.58 ppm = 2H, 3.96-4.42 ppm = 10H, 5.58-5.60 ppm = 2H, 6.04-6.6.05 ppm = 2H, 6.26-6.27 ppm = 2H, 6. 86-6.88 ppm = 4H, 7.12 ppm = 1H, 7.15-7.19 ppm = 6H, 7.42-7.43 ppm = 2H, 7.57-7.58 ppm = 1H, 7.80-7. 81ppm = 2H, 7.91ppm = 1H

Example 1-2 Synthesis of Epoxy Carboxylate Compound (A-2) In a 1 L flask equipped with a stirrer and a reflux tube, 80.2 g of toluene as a diluent solvent and 135. of the epoxy resin obtained in Synthesis Example 1 were used. 6 g (0.6 eq.), 0.56 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and methacrylic acid as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule 51.6 g (0.6 eq.) And 0.56 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 ° C. for 24 hours. The acid value was measured and found to be 2.1 mg · KOH / g. Ended. By this step, a 70% by mass resin solution was obtained.
Next, 250 g of toluene was added to this solution, washed with 100 g of water three times, and the organic layer was concentrated under reduced pressure to obtain 168.5 g of a pale yellow resinous compound (A-2). The structure of the compound was confirmed by measuring ¹ H-NMR.

The physical properties of the compound (A-2) of the present invention are shown below.
Liquid refractive index (D line, 25 ° C.) 1.59
¹ H-NMR
2.01 ppm = 6H, 3.58 ppm = 2H, 3.96-4.42 ppm = 10H, 6.39-6.40 ppm = 2H, 6.47-6.48 ppm = 2H, 6.86-6.88 ppm = 4H, 7.12 ppm = 1H, 7.15-7.19 ppm = 6H, 7.42-7.43 ppm = 2H, 7.57-7.58 ppm = 1H, 7.80-7.81 ppm = 2H, 7. 91ppm = 1H

Synthesis of polycarboxylic acid compound (B) Tetrahydrophthalic anhydride as a polybasic acid anhydride (c) was added to the epoxycarboxylate compound (A-1) obtained in Example 1-1 in the amount shown in Table 1. Toluene was added as a solvent so that the solid content of the reaction solution was 65% by mass. Then, it was made to react at 100 degreeC for 10 hours, and the polycarboxylic acid compound (B-1) solution and the polycarboxylic acid compound (B-2) solution were obtained. Subsequently, this solution was washed 3 times with 100 g of water, and the organic layer was concentrated under reduced pressure to obtain a pale yellow resin-like polycarboxylic acid compound (B). The set acid value in Table 1 means a desired solid content acid value for the finally obtained polycarboxylic acid compound. The polybasic acid anhydride (c), which is a calculation amount for achieving the set acid value, was used.

Comparative Example 1 (Synthesis of Compound (H-1)) Comparison with JP-A-9-272707 A flask equipped with a thermometer, a cooler and a stirrer was subjected to nitrogen gas purge while o-phenylphenol (O-PP Sanko 170 g, Epichlorohydrin 370 g, and 74 g of methanol were charged and dissolved. The mixture was further heated to 70 ° C., and 41 g of flaky sodium hydroxide was added in portions over 90 minutes, and then further reacted at 70 ° C. for 60 minutes. After completion of the reaction, washing was performed twice with 200 g of water to remove the generated salt and the like, and then an excess amount was added in 3 hours with stirring under reduced pressure (˜70 ° C., −0.08 MPa to −0.09 MPa). Epichlorohydrin and the like were distilled off. To the residue, 450 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 g of a 10% by mass aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water until the washing water became neutral. Methyl isobutyl ketone and the like were distilled off from the washed solution under reduced pressure using a rotary evaporator to obtain 217 g of the desired epoxy resin. The obtained epoxy resin had an epoxy equivalent of 233 g / eq. It was liquid at room temperature.
In a 1 L flask equipped with a stirrer and a reflux tube, 139.8 g (0.6 eq.) Of the obtained epoxy resin and 0,2,6-di-t-butyl-p-cresol as a thermal polymerization inhibitor were added. .55 g, 43.3 g (0.6 eq.) Of acrylic acid as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, 0.55 g of triphenylphosphine as a reaction catalyst, and 30 at 98 ° C. The reaction was completed for a period of time, and the acid value measured was 2.4 mg · KOH / g, so the reaction was terminated. By this step, 180 g of a transparent pale yellow resinous compound (H-1) was obtained.

  Table 2 shows the liquid refractive indexes of the compounds of Examples and Comparative Examples and the compounds (H-1), (I-1), and (I-2). The liquid refractive index was calculated by preparing a sample diluted with a solvent so as to vary the obtained compound concentration by three points, measuring the liquid refractive index at three points, and calculating the liquid 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. Measuring wavelength: 589 nm (D line)
(I-1) OPP-1: manufactured by Nippon Kayaku Co., Ltd. (terminal acrylic acid ester of 2-phenylphenol ethylene oxide adduct (I-2) Ogsol EA-200: manufactured by Osaka Gas Chemical Co., Ltd. ( Terminal acrylic acid ester of bisphenolfluorene ethylene oxide adduct)

Example 2 and Comparative Example 2 Compounding of resin composition and preparation of test film obtained in compound (A-1, A-2, B-1, B-2) synthesized in Example 1 and Comparative Example 1 Resin compositions containing the compounds (H-1), (I-1) and (I-2) in the compositions shown in Table 3 (Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3) The compounding amount (g)) was applied to an easily adhesion-treated polyester film (manufactured by Toyobo Co., Ltd .: A-4300, film thickness 188 μm) using a bar coater (No. 20). The polyester film coated with the resin composition is allowed to stand in a drying oven at 80 ° C. for 1 minute, and then is irradiated with ultraviolet light at a conveyance speed of 5 m / min from a distance of 10 cm from a lamp height of 10 cm using a 120 W / cm high-pressure mercury lamp in an air atmosphere. To obtain a film having a cured film (10 to 15 μm).

note)
* 1: PET-30: Nippon Kayaku Co., Ltd., KAYARAD PET-30 (a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate): (B-5)
* 2: Irg. 184 (Irgacure 184): Ciba Specialty Chemicals (1-hydroxycyclohexyl phenyl ketone)
* 3: MEK: Methyl ethyl ketone

Test Example Table 4 shows the evaluation results of the following items for the films obtained in Example 2 or Comparative Example 2.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film was measured using pencil scratching. That is, on a polyester film having a cured film to be measured, a pencil was applied at a 45 degree angle and a 1 kg load was applied from above to scratch about 5 mm to confirm the degree of scratching. Take 5 measurements and count the number of scratches.
Evaluation 5/5: No damage in 5 out of 5 times 0/5: All scratches occurred in 5 times

(Abrasion resistance)
A load of 200 g / cm ² was applied on steel wool # 0000, 10 reciprocations were performed, and the state of scratches was judged visually.
Evaluation 5: Generation of scratches was not observed at all Evaluation 4: Generation of 1 to 5 scratches was observed Evaluation 3: Generation of 6 to 50 scratches was observed Evaluation 2: 51 to 100 scratches were observed Scratch generation was observed Evaluation 1: Coating film peeling was observed

(Adhesion)
In accordance with JIS K 5400, eleven slits were made on the surface of the film at 1 mm intervals in the vertical and horizontal directions to make 100 grids. When the cellophane tape was brought into close contact with the surface and peeled off at once, the number of cells remaining without peeling was displayed.

(curl)
A polyester film having a cured film to be measured was cut into 5 cm × 5 cm, left in an oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four sides that floated on a horizontal table was measured, and the average value was taken as the measured value (unit: mm). At this time, the curl of the base material itself was 0 mm.

(appearance)
Surface cracks, whitening, cloudiness, etc. were judged visually.
Evaluation ○: Good △: Microcracking ×: Significant cracking

  The cured product of the resin composition of the present invention was excellent in hardness, scratch resistance and adhesion as compared with Comparative Example 2, and had the same curl height or lower than Comparative Example 2. From this, it can be seen that the curing shrinkage of the resin composition of the present invention is smaller than the curing shrinkage of Comparative Example 2.

Example 3 Preparation and Evaluation of Active Energy Ray Curing Type Optical Resist 20 g of polycarboxylic acid compound (B-1) obtained in Example 1-3, radical reactive type monomer as reactive compound (C) 5 g of dipentaerythritol hexaacrylate as a body and 1.5 g of Irgacure 184 as an ultraviolet reactive photopolymerization initiator were mixed and dissolved by heating to obtain an optical composition.

This was coated on a quartz plate with a hand applicator so as to have a film thickness of 20 microns at the time of drying, and then dried in an electric oven at 80 ° C. for 30 minutes. After drying, the mask pattern was covered from above the coated material and cured by irradiating with an ultraviolet ray with an irradiation dose of 1000 mJ / cm ² by an ultraviolet vertical exposure apparatus (Oak Seisakusho) equipped with a high-pressure mercury lamp to obtain an optical material. Subsequently, 1 mass% sodium carbonate aqueous solution was sprayed, the unexposed part was melt | dissolved and developed. As a result, a pattern could be formed, indicating that the polycarboxylic acid compound (B) of the present invention has resist suitability.

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

Claims (9)

(Meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, as a compound (b) having both an ethylenically unsaturated group and a carboxy group in the epoxy resin (a) represented by the following general formula (1) , An epoxycarboxylate compound (A) obtained by reacting cinnamic acid or one or more compounds selected from the group consisting of compounds obtained by reacting a saturated or unsaturated dibasic acid with a compound having both an unsaturated group and a hydroxyl group ).

(In the general formula (1), _{R 1} represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, selected from any of the alkoxy group having 1 to 6 carbon atoms, a is represents the number of substituents _{R 1,} 1 Or 2. The epoxycarboxylate compound (A) according to claim 1, wherein R ₁ in the general formula (1) is a hydrogen atom. A polycarboxylic acid compound (B) obtained by reacting the epoxycarboxylate compound (A) according to claim 1 with a polybasic acid anhydride (c). A resin composition comprising the compound (A) according to claim 1 or 2. A resin composition comprising (B) according to claim 3. 6. The resin composition according to claim 4 or 5, comprising a reactive compound (C) other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B). Reactive compound (C) is (poly) ester (meth) acrylate (C-1), urethane (meth) acrylate (C-2), epoxy (meth) acrylate (C-3), (poly) ether (meth) Acrylate (C-4), alkyl (meth) acrylate or alkylene (meth) acrylate (C-5), (meth) acrylate (C-6) having an aromatic ring, (meth) acrylate having an alicyclic structure (C- 7) One or more compounds selected from the group consisting of a maleimide group-containing compound (C-8), a (meth) acrylamide compound (C-9), and an unsaturated polyester (C-10). The resin composition as described. The reactive compound (C) is urethane (meth) acrylate (C-2), alkyl (meth) acrylate or alkylene (meth) acrylate (C-5), and (meth) acrylate (C-6) having an aromatic ring. The resin composition according to claim 6, which is one or more compounds selected from the group consisting of: A cured product of the resin composition according to any one of claims 4 to 8.