JP5222156B2 - Carboxylate resin and resin composition containing the same - Google Patents

Description

  The present invention relates to an unsaturated group-containing compound having a specific structure for the purpose of providing an active energy ray cured product having high heat resistance and a high refractive index. Applications include film forming materials, solder masks in the production of printed (wiring circuit) substrates, plating resists, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, and the like.

In recent years, development of photosensitive materials that are cured with active energy rays and have transparency that has high heat resistance and high refractive index has been promoted in various applications (Patent Documents 1 to 3).
In these applications, in addition to high heat resistance and high refractive index, adhesion to a substrate, hardness of a cured product, solubility in alkali, and the like are required. Depending on the application, additives such as monomers and fillers are often added to the resin. However, by adding these additives, the adhesion to the base material and the decrease in the refractive index are brought about, and the characteristics of the organic material (resin) itself when not adding these cannot be fully expressed. There is a demand for a resin having high adhesion to a substrate, heat resistance and refractive index.

  Patent Document 4 discloses a (meth) acrylate compound of a bisalkylene glycol ether compound of 3,3′-diphenyl-4,4′-dihydroxybiphenyl, which is used as a plastic monomer for optical plastic lenses and optical disks. It is described as being useful. However, since the compound is a monomer having no functional group such as a hydroxyl group or a carboxyl group, physical properties such as adhesion and alkali solubility may not be satisfied. Moreover, the obtained resin is light brown and the addition amount may be limited in the optical field that requires transparency.

  Furthermore, Patent Document 5 discloses an epoxy resin composition for semiconductor encapsulation containing an epoxy resin represented by the following general formula (1), a phenol resin, a curing accelerator and an inorganic filler, and has solder resistance and flame resistance. It is disclosed that it is excellent in performance. Patent Document 6 describes an epoxy resin obtained by reacting 3,3′-diphenyl-4,4′-dihydroxybiphenyl with epichlorohydrin, is colorless and has a high refractive index, and is useful for optical applications. It is stated.

WO2002 / 033447 JP 2004-29042 A JP 2005-274664 A Japanese Patent No. 3606615 JP 2000-248050 A JP 2006-307011 A

  An object of this invention is to provide the photosensitive resin and resin composition which are excellent in transparency, have the high refractive index and high adhesiveness by resin itself, and give the hardened | cured material which has sufficient hardness.

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 composition thereof solve the above-mentioned problems as a result of intensive studies and complete the present invention. It came to. That is, the present invention
(1) A compound (A) obtained by reacting the epoxy resin (a) represented by the general formula (1) with a monocarboxylic acid compound (b) having an ethylenically unsaturated group,
Formula (1)

(式中ｎは０〜５の正数を表す）
で表されるエポキシ樹脂（ａ）のエポキシ基に、エチレン性不飽和基を有するモノカルボン酸化合物（ｂ）を付加したジカルボキシレート樹脂、
（６） ｎが０より大きく１以下である上記（５）に記載のジカルボキシレート樹脂、
（７） エチレン性不飽和基を有するモノカルボン酸化合物（ｂ）が（i）（メタ）アクリル酸、（ii）（メタ）アクリル酸とε−カプロラクトンとの反応生成物または（iii）桂皮酸である上記（５）又は（６）のジカルボキシレート樹脂。
（８） エチレン性不飽和基を有するモノカルボン酸化合物（ｂ）が（メタ）アクリル酸である上記（５）又は（６）に記載のジカルボキシレート樹脂、
（９） 上記（５）に記載のジカルボキシレート樹脂及び光重合開始剤を含む感光性樹脂組成物、
（１０） 一般式（１）

(式中ｎは０〜５の正数を表す）
で表されるエポキシ樹脂（ａ）に、エチレン性不飽和基を有するモノカルボン酸化合物（ｂ）を反応させ、該エポキシ樹脂（ａ）のエポキシ基１当量に対して、該モノカルボン酸化合物（ｂ）を０．８〜１当量を付加させることを特徴とするジカルボキシレート樹脂の製造方法、
（１１） 反応を、不活性な有機溶媒及び触媒の存在下に、反応温度６０℃〜１５０℃で行うことを特徴とする上記（１０）に記載のジカルボキシレート樹脂の製造方法、
（１２）上記（５）に記載のジカルボキシレート樹脂及び光重合開始剤を含む感光性樹脂組成物を光硬化させた硬化物、
に関する。(Where n represents a positive number from 0 to 5),
(2) The monocarboxylic acid compound (b) having an ethylenically unsaturated group is (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid. Compound (A) of
(3) The compound (A) according to (1) or (2), wherein the liquid refractive index is 1.6 or more,
(4) A resin composition comprising the compound (A) according to any one of (1) to (3) above and a photopolymerization initiator (B),
(5) General formula (1)

(Where n represents a positive number from 0 to 5)
A dicarboxylate resin obtained by adding a monocarboxylic acid compound (b) having an ethylenically unsaturated group to the epoxy group of the epoxy resin (a) represented by:
(6) The dicarboxylate resin according to (5), wherein n is greater than 0 and 1 or less,
(7) The monocarboxylic acid compound (b) having an ethylenically unsaturated group is (i) (meth) acrylic acid, (ii) a reaction product of (meth) acrylic acid and ε-caprolactone, or (iii) cinnamic acid The dicarboxylate resin of (5) or (6) above.
(8) The dicarboxylate resin according to (5) or (6), wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group is (meth) acrylic acid,
(9) A photosensitive resin composition comprising the dicarboxylate resin according to (5) and a photopolymerization initiator,
(10) General formula (1)

(Where n represents a positive number from 0 to 5)
The monocarboxylic acid compound (b) having an ethylenically unsaturated group is reacted with the epoxy resin (a) represented by the formula (1), and the monocarboxylic acid compound ( a process for producing a dicarboxylate resin, characterized in that 0.8 to 1 equivalent of b) is added;
(11) The method for producing a dicarboxylate resin according to the above (10), wherein the reaction is performed in the presence of an inert organic solvent and a catalyst at a reaction temperature of 60 ° C. to 150 ° C.
(12) A cured product obtained by photocuring a photosensitive resin composition containing the dicarboxylate resin according to (5) and a photopolymerization initiator,
About.

  The compound (A) of the present invention is a novel carboxylate compound having a 3,3′-diphenyl-4,4′-dihydroxybiphenyl skeleton, an ethylenically unsaturated group and a sensitive hydroxy group in the molecule. A resin composition that is flame retardant, excellent in transparency, and has a high refractive index, and the resin composition containing the resin and a photopolymerization initiator can be exposed and cured by active energy rays, and the resulting cured product Is excellent in adhesion to the substrate, excellent in colorless transparency (see FIG. 1), has a high refractive index, has sufficient hardness, and has high flame retardancy. Further, by applying a liquid obtained by diluting the resin composition with an organic solvent, a photocurable film can be formed, and by exposing and curing the coating film, high adhesion is obtained, and It provides a cured product (cured film) having sufficient hardness and flexibility (softness). Accordingly, the compound (A) of the present invention is a component for film forming materials, solder masks for plating (wiring circuit) board production, plating resists, adhesives, lenses, displays, optical fibers, optical waveguides, holograms and the like. Suitable as

The compound (A) of the present invention obtained in Example 1 and the compound (H) obtained in Comparative Example 1 were each diluted with 70% by weight of toluene, and the transmittance at each wavelength of visible light was measured and plotted. It is a figure which shows a graph.

The epoxy resin (a) represented by the above formula (1) used for producing the compound (A) of the present invention is, for example, the following formula (2):
Formula (2)

It can obtain as a crystal | crystallization by making it crystallize, after making it react with epihalohydrin in presence of an alkali metal hydroxide. The phenol compound (c) represented by the above formula (2) can be synthesized, for example, by the method described in Japanese Patent No. 3606615 (the above Patent Document 4).

In the reaction for obtaining the epoxy resin (a), the alkali metal hydroxide that can be used may be a solid or an aqueous solution. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are allowed to flow out continuously under reduced pressure or normal pressure. May be a method of continuously returning to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 equivalent normally with respect to 1 equivalent of hydroxyl groups of the phenolic compound (c) represented by Formula (2), Preferably it is 0.95-2.0. Is equivalent.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and lithium hydroxide.

  In the reaction for obtaining the epoxy resin (a), a quaternary ammonium salt can be added as a catalyst in order to facilitate the reaction. Examples of quaternary ammonium salts that can be used include tetra-lower alkylammonium halides such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride, and tri-lower alkylbenzylammonium halides. As the halide, bromide or chloride is preferred. Further, examples of lower alkyl include C1-C4 alkyl such as methyl, ethyl, propyl and butyl. The amount of quaternary ammonium salt used is usually 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, based on 1 equivalent of the hydroxyl group of the compound represented by formula (2).

  In the reaction for obtaining the epoxy resin (a), the amount of epihalohydrin used is usually 0.8 to 12 equivalents (mol), preferably 0.9 to 1 equivalent (mol) of the hydroxyl group of the compound represented by formula (2). -11 equivalents (moles). As an epihalohydrin to be used, epichlorohydrin is industrially easy to use. At this time, in order to increase the solubility of the compound represented by the formula (2), alcohols such as methanol, ethanol and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane are added. It is preferable to carry out the reaction.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 4-30 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C., preferably 35 to 80 ° C. The temperature may be constant or may be changed with time. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.

  If necessary, after completion of the reaction, the reaction solution is washed with water and / or the reaction solution is cooled to room temperature, and the salt produced during the reaction is removed by filtering the precipitated salt. During the precipitation of the epoxy resin, there is a possibility that a salt may be mixed in the crystal of the epoxy resin. Therefore, it is preferable to remove the salt generated during the reaction by this operation, preferably by washing the reaction solution with water.

  The crystallization method from the obtained epoxy resin reaction liquid is not particularly specified. For example, various methods such as concentrating and then recrystallizing with a solvent, or adding a poor solvent and reprecipitating. However, in the present invention, the following method is preferable.

  The reaction mixture containing the reaction product, epihalohydrin and the like is heated to remove excess epihalohydrin and the like under reduced pressure (step d). At this time, when the crystals are precipitated and become slurry, the recovery under reduced pressure is stopped (step e), where ketones such as acetone, methyl ethyl ketone (MEK), cyclopentanone (CP), cyclohexanone, or ethyl acetate, Add organic solvents such as esters such as butyl acetate, ethyl butyrate, γ-butyrolactone, carbitol acetate, ethers such as dioxane, THF, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, After the dispersion (step f), an organic solvent such as a water-soluble solvent, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol, and ketones such as acetone is added as necessary (step f). ´), water slowly there Add dropwise (g). The target crystalline epoxy resin can be obtained by filtering and drying (h) the obtained crystals.

  The conditions in the above step and the amount of solvent used vary depending on the solvent used, so the range cannot be defined unconditionally. For example, when epichlorohydrin is used as the epihalohydrin in step d, acetone is used in step f, and methanol is used in step f ′, In step d, it is preferably heated to 50 to 100 degrees, and the degree of vacuum is about -0.05 MPa to -0.095 MPa. The amount of acetone used in step f is preferably 20 to 500% by weight, more preferably 50 to 200% by weight, based on the theoretical yield of the reaction product. The methanol used in step f ′ is preferably 20 to 500% by weight, more preferably 50 to 200% by weight, based on the theoretical yield. The water used in step g is preferably 40 to 1000% by weight based on the theoretical yield. The ratio (weight ratio) of the organic solvent used in (step f) and (step f ′) and the water used in (step g) is (solvent in step f) :( solvent in step f ′) :( step g Water) = 1 to 3: 1 to 3: 1 to about 9 is preferable. Moreover, it is preferable to wash | clean the crystal | crystallization filtered in the process h with alcohol, such as methanol and ethanol, or water.

  Although the epoxy resin (a) obtained as described above varies depending on reaction conditions and the like, it cannot be generally stated, but when synthesized under the above preferred conditions, in the compound represented by the general formula (1), n = It is obtained as a mixture mainly containing a compound of 0 and a small amount of a compound of n = 1 to 5. Therefore, n in General formula (1) is represented by the average value of those mixtures, n represents the positive number of 0-5, Preferably it is 0-1. The method of calculating the value of n (average value) is, for example, after actually measuring the epoxy equivalent, calculating by comparing with the theoretical molecular weight, or analyzing the molecular weight distribution by GPC and calculating the peak area of each n number For example, a method of calculating an average value.

The production of the compound (A) of the present invention can be obtained by reacting the epoxy resin (a) with a monocarboxylic acid compound (b) having an ethylenically unsaturated group (hereinafter referred to as carboxylation reaction). say).
The compound (A) of the present invention is a carboxylate obtained by adding the carboxyl group of the monocarboxylic acid compound (b) to the epoxy group of the epoxy resin (a), and the use of the monocarboxylic acid compound (b). Although mono or dicarboxylate, a mixture thereof, and the like can be obtained depending on the amount and the like, in the present invention, 1 equivalent of monocarboxylic acid compound (b) per 1 equivalent of epoxy group of epoxy resin (a) ( A dicarboxylate obtained by adding a monocarboxylic acid compound (2 mol) to 1 mol of the epoxy resin (a) is preferred.
When a single compound of the epoxy resin (a) as a raw material (for example, an integer compound such as n = 0, 1) can be used, a single carboxylate compound can be obtained. Thus, since the epoxy resin (a) is obtained as a mixture of the epoxy compounds represented by the general formula (1) and used as it is, the compound (A) of the present invention is also a mixture of the corresponding carboxylate compounds. As obtained.
Therefore, the compound (A) of the present application is basically a carboxylate resin in which the carboxyl group of the monocarboxylic acid compound (b) is added to the epoxy group of the epoxy resin (a), more preferably The carboxylate resin is obtained by adding 0.8 to 1 equivalent of the monocarboxylic acid compound (b) to 1 equivalent of an epoxy group.

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group for producing the compound (A) of the present invention include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated. Examples include a reaction product of a dibasic acid and an unsaturated group-containing monoglycidyl compound (ethylenically unsaturated group-containing monoglycidyl compound). A preferable monocarboxylic acid compound (b) is acrylic acid. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, reaction products of (meth) acrylic acid and ε-caprolactone, saturated or unsaturated dibasic acid anhydrides ( Half-esters, saturated or unsaturated dibasic acid and monoglycidyl (meta) which are equimolar reaction products of (meth) acrylate derivatives having one hydroxyl group in one molecule and maleic anhydride, tetrahydrophthalic anhydride, etc. ) Half-esters which are equimolar reactants with acrylate derivatives. As one of the more preferred compounds, the following formula (3)
R1-CH = CH-COOH
(Wherein R1 represents a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom or a methyl group) or a reaction product of (meth) acrylic acid and ε-caprolactone. Can do.
In view of sensitivity when a photosensitive resin composition is used, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is particularly preferable.
In the present invention, the term “(meth) acrylic acid” represents acrylic acid or methacrylic acid.

  This carboxylation reaction can be carried out in the absence of a solvent or can be carried out after dilution with a solvent. Usually, the reaction is preferably carried out in the presence of a solvent. The solvent that can be used here is not particularly limited as long as it is inert to the carboxylation reaction. One preferable example is a solvent having no alcoholic hydroxyl group.

  The usage-amount of a solvent can be suitably adjusted with the viscosity and usage of resin obtained. For example, when the total of the solid content and the solvent content in the carboxylation reaction is 100% by weight, the solvent is used so that the amount of the solvent used is 90 to 0% by weight, more preferably 60 to 5% by weight.

Examples of the solvent having no alcoholic hydroxyl group include ketones such as acetone, ethyl methyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, and ethylene glycol diethyl. Glycol ethers such as ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, Esters such as dialkyl dipinates, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, and various monomers and acid anhydrides of polycarboxylic acid compounds For example, hydroxyl-containing (meth) acrylate (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol ( A half ester that is a reaction product of a polycarboxylic acid compound and an acid anhydride of a polycarboxylic acid compound, and a half ester that is a reaction product of an acryloylmorpholine and an acid anhydride of a polycarboxylic acid compound. Examples of acid anhydrides of acid compounds include succinic anhydride, Maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.).
In addition, the terminal acrylic acid ester of 2-phenylphenol ethylene oxide adduct (eg, OPP-1, OPP-2 manufactured by Nippon Kayaku Co., Ltd.), polyethylene glycol di (meth) acrylate, tripropylene glycol di Di () -caprolactone adduct of (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and hydroxypenic acid neopenglycol meth) acrylate (e.g., manufactured by Nippon Kayaku ^{Co., KAYARAD RTM HX-220, HX} -620 , etc.), pentaerythritol tetra (meth) acrylate, a reaction product of dipentaerythritol and ε- caprolactone Poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol di) Epoxy that is a reaction product of (meth) acrylic acid with glycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. A (meth) acrylate etc. can be mentioned.
Moreover, when the solvent which can be used including the above-mentioned solvent is classified more specifically, a hydrocarbon solvent, an ester solvent, an ether solvent, a ketone solvent and the like can be exemplified. If they are specifically classified and illustrated, examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, and aliphatic hydrocarbons such as hexane, octane and decane. Solvents and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha 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, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.

  Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, 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. Glycol ethers, and cyclic ethers such as tetrahydrofuran.

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

  In addition, the reaction can be carried out in a single or mixed organic solvent such as an ethylenically unsaturated compound (C) (excluding the compound (A) of the present invention) inert to the above reaction. In this case, it is preferable because the reaction solution can be used as it is as a curable composition without separating the reaction product.

Specific examples of the ethylenically unsaturated compound (C) are so-called reactivity such as radical reactive acrylates which are inactive in the carboxylation reaction but react in the curing reaction of the resin composition described later. Monomers or reactive oligomers may be mentioned.
Examples of the acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, Examples include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and biphenyloxyethyl (meth) acrylate.

As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and γ-caprola of hydroxypenic acid neopenglycol Tone adduct di (meth) acrylate, reaction product of dipentaerythritol and γ-caprolactone, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( And (meth) acrylate and its ethylene oxide adduct, and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and its ethylene oxide adduct.
The above solvents can be used alone or as a mixed organic solvent.

  The raw material charge ratio in the reaction is preferably 0.8 to 1.2 equivalents (80 to 120 equivalent%) of the monocarboxylic acid compound (b) with respect to 1 equivalent of the epoxy group of the epoxy resin (a). It is. When deviating from this range, there is a risk of causing gelation during the reaction, or the thermal stability of the finally obtained compound (A) may be lowered.

  During the reaction, it is preferable to use a catalyst in order to promote the reaction. When the catalyst is used, the amount of the catalyst used is 0.1 to 10% by weight with respect to the reaction product. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane Examples include zirconium acid.

  Further, a thermal polymerization inhibitor can be used. Specific examples include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, diphenylpicrylhydrazine, diphenylamine, 3,5-ditertiary butyl-4hydroxytoluene and the like can be mentioned, and the amount used is preferably 0.1 to 10% by weight based on the reaction product.

When the monocarboxylic acid compound (b) is used in the above-mentioned preferable range, the sample has an acid value of 5 mg · KOH / g or less, preferably about 3 mg · KOH / g, while sampling the reaction solution as appropriate. The end point of the reaction is preferably the time point at which: Isolation of the reaction product can be obtained by removing the solvent from the reaction solution by a conventional method such as vacuum distillation.
In this case, the obtained target compound (A) (carboxylate compound) of the present invention is 0.8 to 1 equivalent of the monocarboxylic acid compound (b) relative to 1 equivalent of the epoxy group of the raw material epoxy resin (a). Preferably, it can be obtained as a compound with 0.9 to 1 equivalent added.
Moreover, the said reaction liquid can also be used as a resin composition in this invention, adding a photoinitiator there without isolating the target compound depending on the case.

The compound (A) of the present invention preferably has a liquid refractive index high by the resin alone and a liquid refractive index of 1.6 or more, for example, 1.60 to 1.65. In the present invention, the liquid refractive index is the refractive index of the compound before curing, and for example, D-line (589 nm) can be used although the measurement wavelength varies. All the refractive indexes described in the present specification are measured values at the D line (589 nm).
An apparatus for measuring such a refractive index is common, for example, a multi-wavelength Abbe refractometer manufactured by Atago Co., Ltd. is available. As the measuring method, for example, a liquid compound before being cured can be directly applied, and the angle at which the transmitted light of the light source is refracted can be measured.
As described above, the compound (A) of the present invention is a carboxylate resin in which the monocarboxylic acid compound (b) is added to the epoxy group of the epoxy resin (a). On average, it has 1.6 to 7, preferably 1.8 to 3 hydroxy groups. The dicarboxylate resin basically has a structure in which the monocarboxylic acid compound (b) is added to two epoxy groups of the general formula (1), and the value of n is basically the same as that of the raw material epoxy resin. The same.
The compound (A) of the present invention can be used in various applications as described above together with a photopolymerization initiator, a heat-sensitive polymerization initiator (such as azobisisobutyronitrile) and the like. In the present invention, a photopolymerizable resin composition containing the compound (A) of the present invention and a photopolymerization initiator (B) is one of preferred embodiments.

The resin composition of the present invention contains the compound (A) of the present invention and a photopolymerization initiator (B). The content of the compound (A) in 100 parts by weight of the resin composition of the present invention is preferably 5 to 98 parts by weight, preferably 10 to 96 parts by weight, and in some cases, 10 to 94 parts by weight.
The balance is a photopolymerization initiator and optional additives. In order to take advantage of the characteristics of the resin of the present invention, the resin of the present invention is preferably about 20 to 98% (weight%: the same unless otherwise specified), more preferably, based on the entire solid content of the resin composition. Is 30 to 98%, optionally 40 to 98% or 50 to 98%, and in other cases 20 to 94% (weight%: the same unless otherwise specified), more preferably 30 to 94%. Depending on the case, it is preferable that 40 to 94% or 50 to 94% is contained.

As the photopolymerization initiator (B) contained in the resin composition of the present invention, any one used as a photopolymerization initiator can be used. For example, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl -1-phenyl-propan-1-one (Darocur 1173; manufactured by Ciba Specialty Chemicals), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, Isopro Lucio xanthone, 2,4,6 dichloride phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like. These photopolymerization initiators may be used alone or in combination at any ratio, and may be used in combination with photopolymerization initiation assistants such as amines. Of these photopolymerization initiators, ketone-based polymerization initiators are preferred.
As content of the photoinitiator (B) in the resin composition (100 weight part) of this invention, 0.5-20 weight part is preferable, More preferably, it is 1-10 weight part. In this case, the content of the compound (A) of the present invention is 99.5 to 10 parts by weight, preferably 99 to 20 parts, and the optional component is the balance.
Moreover, depending on the case, content of a photoinitiator (B) is 1-20 weight part, Preferably it is 2-10 weight part, More preferably, it is 4-10 weight part. In this case, the content of the compound (A) of the present invention is 98 to 5 parts by weight, preferably 96 to 10 parts by weight, and the optional component is the balance. Preferred as the optional component is the ethylenically unsaturated compound (C) described below.

The resin composition of this invention can contain a various arbitrary component as needed.
Examples of the main optional component include a photopolymerization initiation aid, an ethylenically unsaturated compound (C) other than the compound (A) of the present invention, other additives, and a diluent as described below. .
Examples of photopolymerization initiation assistants such as amines that can be used in the present invention include diethanolamine, 2-dimethylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester. Etc. The content of the photopolymerization initiation assistant in the resin composition (100 parts by weight) of the present invention is 0 to 5 parts by weight. When the photopolymerization initiation assistant is used in combination, the content in the oil composition composition of the present invention The amount is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

  As a preferable thing of the ethylenically unsaturated compound (ethylenically unsaturated compound other than the compound (A) of this invention) which can be added as needed with the resin composition of this invention, (meth) acrylate is mentioned, for example A monomer, a (meth) acrylate oligomer, etc. are mentioned, You may use them arbitrarily.

(Meth) acrylate monomers as ethylenically unsaturated compounds are classified into monofunctional monomers having one (meth) acrylate group in the molecule and polyfunctional monomers having two or more (meth) acrylate groups in the molecule. it can.
Monofunctional monomers having one (meth) acrylate group in the molecule include, for example, tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meta ) Acrylate, adamantyl (meth) acrylate, phenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxyethyl ( Examples include meth) acrylate, 2-hydroxypropyl (meth) acrylate, and ethyl carbitol (meth) acrylate.

  Examples of the (meth) acrylate monomer having two or more (meth) acrylate groups in the molecule include neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, and hydroxypivalaldehyde-modified tri Methylolpropane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide De-modified pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate.

  These (meth) acrylate monomers may be used singly, in combination of two or more, and in any ratio. The content of the (meth) acrylate monomer in the resin composition (100 parts by weight) of the present invention is 0 to 90 parts by weight, and when the (meth) acrylate monomer is used, 1 to 90 parts by weight is preferable. Preferably it is 5-85 weight part.

  Examples of the (meth) acrylate oligomer as the ethylenically unsaturated compound include urethane (meth) acrylate having a molecular weight of 400 to 10,000 and epoxy (meth) acrylate having a molecular weight of 500 to 10,000.

A urethane (meth) acrylate having a molecular weight of 400 to 10,000 is obtained by a reaction of the following polyhydric alcohol, an organic polyisocyanate, and a hydroxy (meth) acrylate compound.
Examples of the polyhydric alcohol include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and triglyceride. Polyhydric alcohols such as cyclodecane dimethylol and bis- (hydroxymethyl) -cyclohexane; and the polyhydric alcohols and polybasic acids (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid Polyester polyol obtained by reaction with tetrahydrophthalic anhydride, etc .; and caprolactone alcohol obtained by reaction of the polyhydric alcohol with ε-caprolactone; and polycarbonate polyol (for example, 1,6- Hexanediol polycarbonate diol obtained by reacting diphenyl carbonate); and polyether polyols (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.).
Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, and dicyclopentanyl isocyanate.
Examples of the hydroxy (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono (meth) acrylate, hydroxycaprolactone (meth) acrylate, and the like. .
The content of urethane (meth) acrylate having a molecular weight of 400 to 10000 in the resin composition (100 parts by weight) of the present invention is 0 to 90 parts by weight. When the urethane (meth) acrylate is used, 1 to 90 parts by weight. Part is preferred, more preferably 3 to 85 parts by weight.

Although there is no restriction | limiting in particular as said epoxy acrylate of the molecular weight 500-10000, It is preferable to use a bisphenol type epoxy acrylate, for example, bisphenol A type epoxy resin, such as Epicoat ^RTM 802,1001,1004 by Yuka Shell Epoxy Co., Ltd. And epoxy acrylate obtained by reaction of bisphenol F type epoxy resin such as Epicoat ^RTM 4001P, 4002P, 4003P and (meth) acrylic acid (superscript RTM represents a registered trademark). Moreover, you may use the alicyclic epoxy acrylate which hydrogenated the above. The content of the epoxy acrylate having a molecular weight of 500 to 10,000 in the resin composition (100 parts by weight) of the present invention is 0 to 90 parts by weight. When the epoxy acrylate is used, the content in the resin composition of the present invention. Is preferably 1 to 90 parts by weight, more preferably 3 to 85 parts by weight.

  Furthermore, the resin composition of the present invention is a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, and an antioxidant depending on the application. UV absorbers, flame retardants, pigments, dyes, and the like can be used as appropriate.

  Specific examples of the non-reactive compound include a liquid or solid oligomer or resin having low reactivity or non-reactivity, and includes (meth) acrylic acid alkyl copolymer, epoxy resin, liquid polybutadiene, Examples include, but are not limited to, cyclopentadiene derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, and silicon-based oligomers. It is not something.

  Examples of the inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, and glass. , Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon, and the like. 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 can be mentioned.

  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, pigment, and dye that can be used in the resin composition of the present invention can be used. As long as the curability and resin properties are not impaired, the resin can be used without particular limitation.

  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.

The resin composition of the present invention can be diluted with a diluent and used as a coating composition or the like. Diluents include organic solvents, such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, and other commonly used The organic solvent etc. which can be mentioned can be mentioned. One preferred solvent is a ketone solvent. In the coating composition, the resin composition component content other than the organic solvent is preferably about 20% to 80%, more preferably about 30% to 70%.
An example of a preferable coating composition of the present invention will be described below.
20-80% of the resin composition of the present invention
Organic solvent 80-20%
The resin composition of the present invention has the following composition.
Composition of resin composition of the present invention (in 100 parts by weight):
Compound (A) of the present invention 5-99 parts by weight Photopolymerization initiator (B) 1-20 parts by weight Optional component (preferably ethylenically unsaturated compound (C)) The remainder (0-94 parts by weight)

The resin composition of the present invention can be polymerized (cross-linked and cured) by irradiating active energy rays such as ultraviolet rays or visible rays having a wavelength of 180 to 500 nm. It is also possible to cure the heat sensitive initiator (azobisisobutyronitrile or the like) to the resin composition of the present invention by irradiation with energy rays other than ultraviolet rays.
Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short. Examples include arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.
In the present invention, active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. However, in view of a preferred application of the present invention, ultraviolet rays including laser, visible light, or electron beams are preferred.

  The resin composition of the present invention can be used for film-forming materials, solder masks in the production of printed (wiring circuit) substrates, plating resists, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, and the like. The film forming material is used for the purpose of coating the surface of the base material. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink, and offset ink, and coating materials such as hard coat, top coat, overprint varnish, and clear coat. Also, resist materials such as solder resists, etching resists, micromachine resists, other adhesives for laminating, adhesive materials such as adhesives, various adhesives such as adhesives for LEDs, various lenses such as Fresnel lenses, lenticular lenses, It can also be used for various optical materials such as optical fiber core materials, clad materials, optical waveguides and holograms. Furthermore, after applying a resin composition to a peelable base material temporarily and making it into a film, it can be used also as what is called a dry film which is bonded to the originally intended base material and forms a film.

  The method for forming various coating films is not particularly limited, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, It can also be suitably used in various coating methods such as a die coater, curtain coater, and spin coater.

  Hereinafter, the present invention will be described more specifically with reference examples and examples. However, the present invention is not limited to the following examples.

Reference example 1
Synthesis of epoxy resin (a) of general formula (1) Phenol compound (c) (DOQ-O Sanko) represented by the following formula (2) while purging a nitrogen gas purge to a flask equipped with a thermometer, a cooler and a stirrer 169 parts), epichlorohydrin 463 parts and methanol 169 parts were charged, and the former two were dissolved in methanol. Further, the temperature of the solution was heated to 70 ° C., and 41 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 70 ° C. for 60 minutes. After completion of the reaction, the reaction solution was washed twice with 150 parts of water to remove the generated salt and the like, and then stirred under reduced pressure by heating (up to 70 degrees, -0.08 MPa to -0.09 MPa). Excess epichlorohydrin and the like were distilled off over time. When the reaction solution was in a slurry state, the reduced pressure was released, 300 parts of acetone was added thereto, stirred for 30 minutes at reflux, 1500 parts of methanol was added and stirred for 15 minutes, and then 300 parts of water were gradually added. . The precipitated crystals were separated by filtration under reduced pressure to obtain the desired crystalline epoxy resin (n = 0.01 (average value)). Further, the crystal was sufficiently washed with 200 parts of methanol and further 200 parts of water and dried to obtain 191 g of the target epoxy resin (a) as white to pale white powdery crystals. The melting point of the obtained epoxy resin (a) was 98 ° C. Moreover, as a result of analyzing an epoxy equivalent according to JISK7236: 2001, the epoxy equivalent of this epoxy resin (a) was 227 g / eq. From this analysis value, the value of n in the general formula (1) was calculated to be 0.01. Moreover, when the refractive index of this epoxy resin (a) was measured, the refractive index was 1.65. (A sample was dissolved in dimethyl sulfoxide, and its refractive index was measured and calculated at three points. Measuring apparatus: Multi-wavelength Abbe refractometer DR-M2, manufactured by Atago Co., Ltd., measurement wavelength: 589 nm (D line))
Formula (2)

Example 1
Synthesis of Compound (A) of the Present Invention In a 1 L flask equipped with a stirrer and a reflux tube, 128.2 g of toluene as a diluent, epoxy resin (a) obtained in the same manner as in Synthesis Example 1 (n = 0.01 (average value)) is 227.0 g (epoxy equivalent: 1.0 equivalent), and the monocarboxylic acid compound (b) having an ethylenically unsaturated group is 72.06 g of acrylic acid (molecular weight 72.06). (1.0 equivalent), 2.56 g of 2,6-ditert-butyl-p-cresol as a thermal polymerization inhibitor and 1.28 g of triphenylphosphine as a reaction catalyst were charged at a temperature of 100 ° C. for 24 hours. The reaction was performed to obtain a solution containing 70% by weight of the compound (A) of the present invention. The acid value of the solution was measured and found to be 0.3 mg · KOH / g.
Next, 570 g of toluene was added to this solution, washed with 100 g of water three times, and the organic phase was concentrated under reduced pressure to obtain a pale yellow resinous compound (A). The epoxy equivalent of this resinous compound (A) is 62,000 g / eq. Met. From this analysis value, the raw material epoxy group reaction rate (acrylic acid introduction rate) was calculated to be 99.3%.
The refractive index of this resin at 25 ° C. was directly measured using the same measuring apparatus as in Reference Example 1. As a result, it was 1.616.
Moreover, when proton NMR was measured, the following peaks were obtained.

H-NMR
3.90-4.50 ppm = 10H, 5.83 ppm = 2H, 6.15 ppm = 2H, 6.42 ppm = 2H, 6.90-7.65 ppm = 16H

Comparative Example 1 (H)
Under a nitrogen atmosphere, 67.6 g (0.2 mol) of a phenol compound (DOQ-O Sanko Co., Ltd., molecular weight: 338.1) of the above formula (2) in a 2 L flask equipped with a stirrer and a reflux dehydrator, toluene Was charged with 600 ml and ethylene carbonate (molecular weight: 88.06) 61.6 g (0.70 mol). To the obtained liquid, 8 g of anhydrous potassium carbonate powder was added at 90 to 110 ° C. with stirring, and reacted for 5 hours as it was. The reaction mixture is cooled, the precipitate is filtered off, washed with water and methanol, dried at 75 ° C., and the ethylene oxide adduct of the phenol compound (c) represented by the above formula (2) is converted into white crystals. 71.0 g was obtained.
Subsequently, 42.7 g (0.10 mol) of the ethylene oxide adduct (molecular weight: 426.5) obtained above was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator. ), 17.3 g (0.24 mol) of acrylic acid (molecular weight: 72.06), 0.35 g of paratoluenesulfonic acid monohydrate, 0.14 g of hydroquinone, and 60 g of toluene, and the reaction temperature was 100 The reaction was carried out while azeotropically distilling off the produced water with a solvent at from C to 115 ° C., and when the produced water reached 3.6 ml, the reaction was terminated. The reaction mixture was dissolved in 100 g of toluene, neutralized with 25% aqueous sodium hydroxide solution, and then washed 3 times with 20 g of 15% brine. The solvent was distilled off under reduced pressure to obtain 51.6 g of an ethylene oxide acrylate compound (H) of the phenol compound (c) represented by the brown resin-like formula (2). The refractive index of this resin at 25 ° C. was measured and found to be 1.614.

Further, FIG. 1 shows data obtained by diluting the compounds obtained in Example 1 and Comparative Example 1 with 70% by weight of toluene and measuring the transmittance with visible light.
As can be seen from FIG. 1, the compound (A) of the present invention has a high and constant light transmittance of 70 to 80% over a wavelength of 450 to 800 nm, and it is clear that there is no coloring and high transparency. .
In this example, by reacting according to Example 1 except that 148 g of cinnamic acid (molecular weight 148) was used instead of acrylic acid, the epoxy group of the epoxy resin of the general formula (1) A carboxylate resin to which cinnamic acid has been added can be obtained.
Moreover, by using a reaction according to Example 1 except that a reaction product of acrylic acid and ε-caprolactone is used instead of acrylic acid, the epoxy group of the epoxy resin of the general formula (1) A carboxylate resin to which a reaction product is added can be obtained.

Example 2 and Comparative Example 2
In addition, the compounds obtained in Example 1 and Comparative Example 1 were each diluted with 50% by weight of MEK (2-butanone), and Irgacure 184 (manufactured by Ciba Specialty Chemicals: 1-hydroxycyclohexyl) as a photopolymerization initiator. 3% by weight of phenylketone) was added to obtain a diluted solution (coating composition) of the resin composition of the present invention.
Next, these solutions were applied to an easy adhesion treatment polyester film (manufactured by Toyobo Co., Ltd .: A-4300, film thickness 188 μm) using a bar coater (No. 20), and left in a drying oven at 80 ° C. for 1 minute. While transporting the film at a transport speed of 5 m / min in an air atmosphere, a 120 W / cm high-pressure mercury lamp is used to irradiate ultraviolet rays from a distance of a lamp height of 10 cm to cure the coated film (10 A film having ˜15 μm) was obtained.

  With respect to the obtained film, according to JIS K 5400, 100 grids were made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the film. Next, Table 1 shows the number of cells remaining without peeling when the cellophane tape was adhered to the surface and then peeled off at once.

Table 1
Film Number of remaining squares Film of Example 2 83
(Film having a cured film of compound (A) obtained in Example 1)
Film of Comparative Example 2 24
(Film having a cured film of compound (H) obtained in Comparative Example 1)

  From the above results, the compound (A) of the present invention is a resin having excellent transparency, a high refractive index, and a cured film of the resin composition of the present invention containing the compound (A) of the present invention. Has high adhesion.

  The compound (A) of the present invention is excellent in transparency and has a high refractive index, and the resin composition containing it has high adhesion in the formation of a coating film by exposure and curing with active energy rays, And the hardened | cured material which has sufficient hardness is given. Therefore, the photosensitive resin is suitable as a component for film forming materials, solder masks for plating (wiring circuit) substrates, plating resists, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, etc. Yes.

Claims (12)

A compound (A) obtained by reacting the epoxy resin (a) represented by the general formula (1) with a monocarboxylic acid compound (b) having an ethylenically unsaturated group,
Formula (1)

(In the formula, n represents a positive number of 0 to 5).   The monocarboxylic acid compound (b) having an ethylenically unsaturated group is (i) (meth) acrylic acid, (ii) a reaction product of (meth) acrylic acid and ε-caprolactone, or (iii) cinnamic acid. The compound (A) according to claim 1.   The compound (A) according to claim 1 or 2, wherein the liquid refractive index is 1.6 or more.   A resin composition comprising the compound (A) according to any one of claims 1 to 3 and a photopolymerization initiator (B). General formula (1)

(Where n represents a positive number from 0 to 5)
The dicarboxylate resin which added the monocarboxylic acid compound (b) which has an ethylenically unsaturated group to the epoxy group of the epoxy resin (a) represented by these.   6. The dicarboxylate resin according to claim 5, wherein n is greater than 0 and 1 or less.     The monocarboxylic acid compound (b) having an ethylenically unsaturated group is (i) (meth) acrylic acid, (ii) a reaction product of (meth) acrylic acid and ε-caprolactone, or (iii) cinnamic acid. Item 7. The dicarboxylate resin according to Item 5 or 6.   The dicarboxylate resin according to claim 5 or 6, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group is (meth) acrylic acid.   A photosensitive resin composition comprising the dicarboxylate resin according to claim 5 and a photopolymerization initiator. General formula (1)

(Where n represents a positive number from 0 to 5)
The monocarboxylic acid compound (b) having an ethylenically unsaturated group is reacted with the epoxy resin (a) represented by the formula (1), and the monocarboxylic acid compound ( A method for producing a dicarboxylate resin, characterized in that 0.8 to 1 equivalent of b) is added.   The method for producing a dicarboxylate resin according to claim 10, wherein the reaction is performed at a reaction temperature of 60 ° C. to 150 ° C. in the presence of an inert organic solvent and a catalyst.   Hardened | cured material which photocured the photosensitive resin composition containing the dicarboxylate resin of Claim 5, and a photoinitiator.

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