JP2017128671A - Epoxy resin, reactive carboxylate compound, curable resin composition using the same, and use of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent photosensitive resin composition that is cured by active energy rays or the like such as UV rays, shows excellent photosensitivity and good developability, and gives a cured product having a sufficiently cured state as well as flexibility, toughness, flame retardancy and color pigment dispersibility.SOLUTION: The present invention provides: an epoxy resin (A) obtained by allowing an epoxy resin (a) represented by general formula (1) to react with a compound (b) having two or more phenolic hydroxyl groups in one molecule; a reactive epoxy carboxylate compound (B) obtained by allowing the epoxy resin (A) to react with a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule; a reactive epoxy carboxylate compound (B') obtained by allowing the epoxy resin (A) and a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule to react with a compound (d) having a hydroxyl group and a carboxy group in one molecule; and a reactive polycarboxylic acid compound (C) and a reactive polycarboxylic acid compound (C') obtained by allowing the reactive epoxy carboxylate compound (B)/(B') to react with a polybasic acid anhydride (e).SELECTED DRAWING: None

Description

  The present invention relates to a reactive epoxy carboxy obtained by reacting an epoxy resin (A) having a polycyclic hydrocarbon group with a compound (c) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. The present invention relates to a rate compound (B) and a reactive epoxycarboxylate compound (B ′) obtained by reacting the reactive epoxycarboxylate compound (B) with a compound (d) having both a hydroxyl group and a carboxy group in one molecule. Moreover, the reactive polycarboxylic acid compound (C) or the reactive polycarboxylic acid compound (C) obtained by reacting the reactive epoxycarboxylate compound (B) or (B ′) with the polybasic acid anhydride (e). ') Regarding. Further, at least one selected from a reactive epoxy carboxylate compound (B), a reactive epoxy carboxylate compound (B ′), a reactive polycarboxylic acid compound (C), and a reactive polycarboxylic acid compound (C ′). The active energy ray-curable resin composition containing, and a cured product thereof.

  In the solder resist that covers the circuit of the printed wiring board, the adhesion to the substrate, the high insulation, the electroless gold plating property, and the cured material properties are required while maintaining the heat resistance and the thermal stability.

  As a solder resist material (film forming material), Patent Document 1 discloses a carboxylate compound as a material having excellent developability while having a low acid value. It is further disclosed that this compound has resist ink suitability. The acid-modified epoxy acrylate described in Patent Document 2 exhibits high toughness after curing, and has been studied as a solder resist.

  In Patent Document 3, carbon black or the like is dispersed in acid-modified epoxy acrylate, and a black matrix resist used for a liquid crystal display panel or the like is examined. In the black matrix resist, it is required that a colored pigment such as carbon black has good affinity with the resin and the pigment is dispersed. This is because even if the color pigment is at a high concentration, it is developed without a pigment residue.

  Conventional acid-modified epoxy acrylates, particularly acid-modified epoxy acrylates having a biphenyl skeleton exhibit relatively good dispersibility. However, due to the good affinity with the pigment and the rigid structure of the skeleton, when the pigment dispersion is made, there is a problem that the dispersion is agglomerated in a pseudo manner and the stability is not good.

  The acid-modified epoxy acrylate compound of the epoxy resin described in Patent Document 4 is not known.

Japanese Patent Laid-Open No. 06-324490 JP-A-11-140144 JP 2005-055814 A JP 2013-043958 A International Publication No. 2009/028479

  Although the curable resin composition containing the acid-modified epoxy acrylate can obtain a relatively tough cured product, it is not reliable as a material that requires extremely high reliability such as transportation equipment. Furthermore, there is a need for acid-modified epoxy acrylate compounds that have better dispersibility of colored pigments, especially carbon black, and that have good development characteristics even at high pigment concentrations. At this time, it is necessary to have a relatively high molecular weight and appropriate developability.

In order to solve the above-mentioned problems, the present inventors obtained a reaction between an epoxy resin (a) having a polycyclic hydrocarbon group and a compound (b) having two or more phenolic hydroxyl groups in one molecule. Reactive epoxy carboxylate compound (B) obtained by reacting an epoxy resin (A) obtained and a compound (c) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group, reactive epoxy carboxylate Reactive epoxycarboxylate compound (B ′) obtained by reacting compound (B) with compound (d) having both a hydroxyl group and a carboxy group in one molecule, and further polybasic acid anhydride (d) It has been found that the reactive polycarboxylic acid compounds (C) and (C ′) obtained by the reaction have particularly excellent resin properties.
Furthermore, it has been found that the reactive epoxycarboxylate compound (B) and the reactive polycarboxylic acid compound (C) have a good affinity for the color pigment, and the composition containing these compounds is high. It has been found that the resist material has good developability even at a pigment concentration.

  The present invention relates to an epoxy resin (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having two or more phenolic hydroxyl groups in one molecule.

  In general formula (1), Ar is each independently either (2) or (3), and the molar ratio of (2) and (3) is (2) / (3) = 1-3. . n is the number of repetitions, and is a positive number from 0 to 5. G represents a glycidyl group.

Furthermore, the present invention relates to a reactive epoxycarboxylate compound (B) obtained by reacting the epoxy resin (A) with a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule. .
Further, the present invention relates to a reactive polycarboxylic acid compound (C) obtained by reacting the carboxylate compound (B) with a polybasic acid anhydride (e).
Further, the present invention relates to a reactive epoxycarboxylate compound (B ′) obtained by reacting the reactive epoxycarboxylate compound (B) with a compound (d) having both a hydroxyl group and a carboxy group in one molecule.
Further, the present invention relates to a reactive polycarboxylic acid compound (C ′) obtained by reacting the carboxylate compound (B ′) with a polybasic acid anhydride (e).
Furthermore, it is related with the active energy ray hardening-type resin composition containing the said carboxylate compound (B).
Furthermore, it is related with the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (C).
Furthermore, the present invention relates to an active energy ray-curable resin composition containing the carboxylate compound (B) and / or (C).
Furthermore, it is related with the active energy ray hardening-type resin composition containing the said carboxylate compound (B ').
Furthermore, the present invention relates to an active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (C ′).
Furthermore, it is related with the active energy ray hardening-type resin composition containing the said carboxylate compound (B ') and / or (C').
Further, two or more kinds selected from a reactive epoxy carboxylate compound (B), a reactive epoxy carboxylate compound (B ′), a reactive polycarboxylic acid compound (C), and a reactive polycarboxylic acid compound (C ′) The present invention relates to an active energy ray-curable resin composition.
Furthermore, it is related with the said active energy ray hardening-type resin composition containing a reactive compound (D).
Furthermore, the present invention relates to the active energy ray-curable resin composition containing a color pigment.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a molding material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a film forming material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a resist material composition.
Furthermore, it is related with the hardened | cured material of the said active energy ray hardening-type resin composition.
Furthermore, the present invention relates to an article overcoated with the cured product.
Furthermore, it is related with the manufacturing method of the epoxy resin (A) with which the epoxy resin (a) represented by the said General formula (1) and the compound (b) which has two or more phenolic hydroxyl groups in 1 molecule are made to react.
Furthermore, a method for producing a reactive epoxycarboxylate compound (B), wherein the epoxy resin (A) is reacted with a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule. About.
Further, the epoxy resin (A) has a compound (c) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule, and a compound (d) having both a hydroxyl group and a carboxy group in one molecule. Relates to a process for producing a reactive epoxycarboxylate compound (B ′).
Furthermore, it is related with the manufacturing method of the reactive polycarboxylic acid compound (C) which makes the said carboxylate compound (B) and polybasic acid anhydride (e) react.
Furthermore, it is related with the manufacturing method of the reactive polycarboxylic acid compound (C ') which makes the said carboxylate compound (B') and polybasic acid anhydride (e) react.

  The acid-modified compound of an epoxy resin having a polycyclic hydrocarbon group having a specific structure according to the present invention has a good affinity with a color pigment. The resin composition containing the acid-modified compound has excellent resin properties even when the solvent is simply dried. In addition, the cured product obtained by curing the resin composition of the present invention with an active energy ray such as ultraviolet rays has thermal and mechanical toughness, good storage stability, and further, high temperature and high humidity and cold shock. High reliability to withstand. Therefore, the resin composition of the present invention is suitable for molding materials, film forming materials, and resist materials.

  Due to its high affinity with colored pigments, the acid-modified compound of the present invention and the composition containing the acid-modified compound exhibit good developability even at high pigment concentrations, and resist materials for color resists and color filters, particularly black Suitable for matrix materials.

  The acid-modified compound of the present invention and the composition containing the acid-modified compound are particularly reliable because of thermal and mechanical toughness, good storage stability, and high reliability withstanding high temperature and high humidity and thermal shock. Are used for applications such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

  The epoxy resin (a) used in the present invention is a phenol / resorcin aralkyl type epoxy resin represented by the following general formula (1).

  In general formula (1), Ar is each independently either (2) or (3), and the molar ratio of (2) and (3) is (2) / (3) = 1-3. . n is the number of repetitions, and is a positive number from 0 to 5. Each G is independently a glycidyl group.

  The epoxy resin (a) is commercially available as NC-3500 series from Nippon Kayaku Co., Ltd. Although it does not specifically limit when synthesize | combining an epoxy resin (a), For example, according to the reaction conditions described in patent document 4, it can obtain suitably.

  The epoxy resin (A) of the present invention can be obtained by reacting an epoxy resin (a) with a compound (b) having two or more phenolic hydroxyl groups in one molecule.

  Examples of the compound (b) having two or more phenolic hydroxyl groups in one molecule include those having one aromatic ring in one molecule, those having two or more aromatic rings in one molecule, In the present invention, there is no particular limitation. Examples of those having one aromatic ring in one molecule include hydroquinone, resorcinol, biphenol, dihydroxynaphthalene, trihydroxynaphthalene, tetramethylbiphenol, ethylidene bisphenol, bisphenol A, bisphenol F, bisphenol S, cyclohexylidene bisphenol (bisphenol). Z), dimethylbutylidene bisphenol, 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol], 4,4 ′-(1-phenylethylidene) bisphenol, 5,5 ′-(1- Methylethylidene) bis [1,1′-biphenyl-2-ol], naphthalenediol, dicyclopentadiene-modified bisphenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Reaction products of Kisaido and hydroquinone. Moreover, the compound which has a C1-C4 alkyl group or a phenyl group as a substituent in the aromatic nucleus of these compounds is also mentioned.

  As a compound (b) having two or more phenolic hydroxyl groups in one molecule having two or more aromatic rings in one molecule, resorcin / phenol novolak resin, phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin Modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol Trifunctional or higher functional phenolic compounds such as co-condensed novolak resins, naphthol-cresol co-condensed novolak resins and non-phenol phenol novolak resins It is possible to use. In this invention, the phenol (b-1) represented by Formula (4) which is a raw material of an epoxy resin (a) is preferable.

  In general formula (4), Ph is each independently either (5) or (6), and the molar ratio of (5) and (6) is (5) / (6) = 1-3. . n is the number of repetitions, and is a positive number from 0 to 5.

  The method for synthesizing the epoxy resin (A) is also included in the present invention.

  The method for synthesizing the epoxy resin (A) used in the present invention is not limited, but, for example, two or more phenolic compounds per molecule with respect to 1 mol of the epoxy group of the phenol / resorcin aralkyl type epoxy resin (a). It reacts so that the hydroxyl group of the compound (b) which has a hydroxyl group may be 0.01-0.3 mol.

  The reaction between the epoxy resin (a) and the compound (b) having two or more phenolic hydroxyl groups in one molecule uses a catalyst if necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; triphenylphosphine, diphenylphos Organic phosphines such as tin and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4 -Tetraphenylboron salts such as methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The amount used in the case of using these catalysts depends on the kind of the catalyst, but is generally 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm, if necessary, based on the total resin amount. In this reaction, since the reaction proceeds without adding a catalyst, it may be appropriately used in accordance with the preferred reaction temperature and amount of the reaction solvent.

  In the method of synthesizing the epoxy resin (A), the reaction can be performed without using a solvent, or the reaction can be performed by diluting with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for this reaction. In addition, in the case of producing using a solvent in the next step, carboxylation reaction, and further in the next step, acid addition reaction, the next step is performed directly without removing the solvent, provided that both reactions are inert. It can also be used for the reaction in the process.

  Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.

  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, such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as 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, cyclohexanone, and isophorone.

  In addition, the reaction can be carried out alone or in a mixed organic solvent such as other reactive compounds (D) described later. In this case, when it is used as a curable composition, it can be used directly as a composition, which is preferable.

  The usage-amount of a solvent is 0-300 mass parts with respect to the total resin mass, Preferably it is 0-100 mass parts.

  The reaction temperature and reaction time must be appropriately selected depending on the resin concentration and the amount of catalyst, and cannot be generally defined, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is preferable that the reaction time is short from the viewpoint of productivity. Moreover, reaction temperature is 0-250 degreeC normally, Preferably it is 30-200 degreeC.

  After completion of the reaction, the concentration of the solution of the epoxy resin solution obtained using the solvent can be adjusted as necessary, and the solution can be transferred to the next carboxylation step as a solution containing the epoxy resin (A). If necessary, the catalyst or the like may be removed by washing with water, and the solvent may be distilled off under heating and reduced pressure to isolate the epoxy resin (A) and proceed to the next step.

  The epoxy resin (A) used in the present invention can have a branched structure in addition to a linear structure when Ar is resorcin. When branched, the glycidyl group on the resorcin group reacts with other glycidyl groups to form new bonds. In the case where Ar is resorcin, a branched chain may be further generated from the branched chain. For this reason, the structure of an epoxy resin (A) cannot be determined uniquely, but can take a wide variety of structures for each molecule.

  Next, the carboxylate-forming step of the epoxy resin (A) will be described. This step is a production method for obtaining the reactive carboxylate compound (B) and the reactive carboxylate compound (B ′), and these are also included in the present invention.

  In this reaction, by reacting the epoxy resin (A) with a compound (c) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule, a reactive carboxylate compound (B ) In addition, compound (c) having both one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule and compound (d) having both a hydroxyl group and a carboxy group in one molecule in epoxy resin (A) To obtain a reactive carboxylate compound (B ′).

  The compound (c) having both one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule shown here is used for imparting reactivity to active energy rays. Such compounds (c) include monocarboxylic acid compounds and polycarboxylic acid compounds.

  Examples of the monocarboxylic acid compound include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, (meth) acrylic acids include, for example, (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 A half-reaction product of a (meth) acrylate derivative having one hydroxyl group in the molecule and a half-ester reaction product, a half-ester reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative. Examples include esters.

  Examples of polycarboxylic acid compounds include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters as equimolar reactants, glycidyl (meth) having a saturated or unsaturated dibasic acid and a plurality of epoxy groups. And half-esters which are equimolar reactants with acrylate derivatives.

  Of these, most preferable are (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when an active energy ray-curable resin composition is used. As the compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in one molecule, those having no hydroxyl group in the compound are preferable.

  The compound (d) having one or more hydroxyl groups and one or more carboxy groups in one molecule used in the present invention is used for the purpose of introducing a hydroxyl group into the carboxylate compound. These include compounds having one hydroxyl group and one carboxy group in one molecule, compounds having two or more hydroxyl groups and one carboxy group in one molecule, one or more hydroxyl groups and two in one molecule. There are compounds having both of the above carboxy groups.

  Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like. Examples of the compound having two or more hydroxyl groups and one carboxy group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the compound having one or more hydroxyl groups and two or more carboxy groups in one molecule include hydroxyphthalic acid.

  Among these, those having two or more hydroxyl groups in one molecule are preferable in view of the effects of the present invention. Furthermore, it is preferable that the carboxyl group is one in one molecule in view of the stability of the carboxylation reaction. Most preferably, it has two hydroxyl groups and one carboxy group in one molecule. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As the compound (d) having one or more hydroxyl groups and one or more carboxy groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferable.

  Of these, considering the stability of the reaction between the epoxy resin (A) and (c) and (d), it is preferable that (c) and (d) have one carboxy group. Even when (c) or (d) (monocarboxylic acid) having a carboxy group and (c) or (d) (polycarboxylic acid) having two or more carboxy groups are used in combination, the total molar amount of monocarboxylic acid / The value represented by the total molar amount of the polycarboxylic acid is preferably 15 or more.

  The charge ratio of the epoxy resins (A) and (c) in this reaction or the charge ratio of the total carboxylic acids of (c) and (d) is appropriately changed depending on the application. When all the epoxy groups of the epoxy resin (A) are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the reactive carboxylate compound (B) or (B ′) is high. When there is no unreacted epoxy group, the reactivity of the reactive carboxylate compound (B) or (B ′) depends on the introduced double bond.

  On the other hand, the charge ratio of (c) or the charge amounts of (c) and (d) is reduced to leave unreacted epoxy groups, the reactivity of the introduced double bond, and the reactivity of the unreacted epoxy groups For example, it is possible to use a polymerization reaction or a thermal polymerization reaction by a photocation catalyst in a composite manner (composite curing). However, in this case, care must be taken in the storage of the reactive carboxylate compound (B) or (B ′) and the examination of the production conditions.

  When producing the reactive carboxylate compound (B) or (B ′) having no unreacted epoxy group, an amount of (c) or (c) and (c) sufficient for the epoxy group of the epoxy resin (A) to react. d) may be used. In this invention, it is preferable that the sum total of (c) or (c) and (d) is 90-120 equivalent% with respect to 1 equivalent of the said epoxy resin (A). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound is too large, excess carboxylic acid compounds (c) or (c) and (d) remain, which is not preferable.

  Moreover, when manufacturing the reactive carboxylate compound (B) or (B ') which has an unreacted epoxy group, (c) or (c) and (d) of the quantity which the epoxy group of an epoxy resin (A) remains. May be used. In this invention, it is preferable that the sum total of (c) or (c) and (d) is 20-90 equivalent% with respect to 1 equivalent of the said epoxy resin (A). When the amount of the carboxylic acid compound charged is too small, the efficiency of the composite curing is lowered. In this case, sufficient attention is paid to gelation during the reaction and stability with time of the reactive carboxylate compound (B) and the reactive carboxylate compound (B ′).

  When producing the reactive carboxylate compound (B ′), the compound (c) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups, and one or more hydroxyl groups and one or more carboxy groups are combined. The use ratio of the compound (d) is such that (c) :( d) is 9: 1 to 1: 9, and more preferably 4: 6 to 8: 2 in terms of molar ratio to the carboxy group. Within this range, it is possible to prevent a decrease in sensitivity when (c) is too small, and it is possible to prevent the effect of (d) when (d) is too small from being diluted. In the present carboxylation reaction, there is no particular limitation on the order of preparation of (c) and (d).

  The present carboxylation reaction does not necessarily require a solvent, but may be diluted with a solvent. As the solvent that can be used in the present invention, the solvent that can be used in the present carboxylation reaction may be the same as that used in the synthesis of the epoxy resin (A), and exhibits a reaction with respect to the carboxylation reaction. If there is no solvent, there will be no limitation in particular. Although the usage-amount of a solvent is suitably adjusted with the viscosity and usage of resin obtained, it is 10-70 mass% of the total amount of a reaction material, Preferably it is 20-50 mass%.

  In addition, the reaction can be performed in a single or mixed organic solvent such as a reactive compound (D) other than (A), (B) or (B ′), (C) or (C ′). In this case, when used as a curable composition, it can be used directly as a composition.

  During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is the amount of the reactant, that is, the above-described epoxy compound (A), one or more polymerizable ethylenically unsaturated groups and one or more. It is 0.1-10 mass% with respect to the total amount of the compound (c) which has a carboxy group, and the reaction material which added the solvent etc. depending on the case. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mg · KOH / g or less, preferably 2 mg · KOH / g or less, while sampling appropriately.

  As a preferable molecular weight range of the reactive carboxylate compounds (B) and (B ′) thus obtained, the polystyrene-equivalent weight average molecular weight in GPC is in the range of 1,000 to 30,000, more preferably 1,500. To 20,000. When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is larger than this, the viscosity becomes high and coating or the like becomes difficult.

  Next, the acid addition step will be described. In the acid addition step, a carboxy group is introduced into the reactive carboxylate compound (B) or (B ′) obtained in the previous step as necessary to obtain a reactive polycarboxylic acid (C) or (C ′). It is done for the purpose. As a reason for introducing a carboxy group, for example, in applications where resist patterning or the like is required, the active energy ray non-irradiated part is given solubility in alkaline water, and adhesion to metals, inorganic substances, etc. is given. It is introduced with the purpose of. Specifically, a carboxyl group is introduced through an ester bond by addition reaction of a polybasic acid anhydride (e) to a hydroxyl group generated by a carboxylation reaction.

  As specific examples of the polybasic acid anhydride (e), for example, any compound having an acid anhydride structure in one molecule can be used. However, the alkaline aqueous solution developability, heat resistance, hydrolysis resistance and the like can be used. Excellent succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Acid is particularly preferred.

  The reaction for adding the polybasic acid anhydride (e) can be performed by adding the polybasic acid anhydride (e) to the carboxylation reaction solution. The amount added is appropriately changed according to the application.

  When the polycarboxylic acid compound (C) or (C ′) of the present invention is to be used as an alkali development type resist, the reactive polycarboxylic acid compound (e) finally obtained from the polybasic acid anhydride (e) ( C) or (C ′) is charged with a calculated value such that the solid content acid value (based on JISK5601-2-1: 1999) is 30 to 120 mg · KOH / g, preferably 40 to 105 mg · KOH / g. If the solid content acid value is within this range, the developability of the aqueous solution of the active energy ray-curable resin of the present invention is good. That is, good developability in an aqueous alkali solution means good patternability and a wide control range for overdevelopment, and no excess acid anhydride remains.

  In the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a carboxylate obtained from the reaction product, that is, the epoxy resins (A), (c) and / or (d). It is 0.1-10 mass% with respect to the total amount of the reaction material which added the compound and other basic acid anhydride (e), the solvent, etc. by the case. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples include zirconium acid.

  This acid addition reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used in the acid addition reaction may be the same as that used in the synthesis and carboxylation reaction of the epoxy resin (A), and is not particularly limited as long as it does not react with the acid addition reaction. Absent. In addition, when it is produced using a solvent in the carboxylation reaction that is the previous step, it must be directly subjected to the acid addition reaction that is the next step without removing the solvent, provided that no reaction is exhibited in both reactions. You can also. Although the usage-amount of the solvent in this reaction is suitably adjusted with the viscosity and usage of obtained resin, it is 10-70 mass% of the total amount of a reaction material, Preferably it is 20-50 mass%.

  In addition, it can carry out in a single or mixed organic solvent, such as the reactive compound (D) mentioned later. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor.

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

  Specific examples of the reactive compound (D) that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. Can be mentioned.

  Examples of acrylates that can be used 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, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (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 Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide, “ SyraCure UVR-6110 "), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as" ELR-4206 "manufactured by Union Carbide), limonene dioxide (Daicel Chemical Industries) "Celoxide 3000", etc.), allyl cyclohexylene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy compound) Rohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (D) is most preferably a radical curable acrylate. In the case of the cationic type, the carboxylic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.

  One or more selected from the reactive carboxylate compounds (B) and (B ′), the reactive polycarboxylic acid compounds (C) and (C ′) of the present invention, and (B) and (B ′ ), (C), and a reactive compound (D) different from (C ′) can be mixed to obtain the active energy ray-curable resin composition of the present invention. At this time, you may add another component suitably according to a use.

  The active energy ray-curable resin composition of the present invention is one selected from reactive carboxylate compounds (B) and (B ′), reactive polycarboxylic acid compounds (C) and (C ′) in the composition. 97 to 5% by mass of the above, preferably 87 to 10% by mass, and 3 to 95% by mass of the reactive compound (D) different from (B), (B ′), (C) and (C ′), preferably Contains 3 to 90% by mass. The active energy ray-curable resin composition of the present invention may contain other components up to about 70% by mass of the total amount of the resin composition as necessary.

  The reactive carboxylate compound (B) or (B ′) or the reactive polycarboxylic acid compound (C) or (C ′) of the present invention is appropriately selected depending on the use of the active energy ray-curable resin composition of the present invention. Can be used properly. For example, in the case of a solvent developing type in which the same solder resist application is not developed and a pattern is formed by a printing method or an unreacted site is washed away by a solvent or the like, the carboxylate compound (B) and / or (B ′ In the case of developing with alkaline water, the reactive polycarboxylic acid compound (C) and / or (C ′) is used. In general, the alkaline water development type is more likely to form a fine pattern, and therefore the reactive polycarboxylic acid compound (C) and / or (C ′) is often used for this purpose. Of course, (B), (B ′), (C), (C ′) may be used in any combination depending on the required application / performance.

  The active energy ray-curable 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, gamma rays, and laser rays, and particle rays such as α rays, β rays, and electron beams. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The color pigment that can be used in the present invention is used to make the active energy ray resin composition of the present invention a coloring material. The reactive carboxylate compounds (B) and (B ′), the reactive polycarboxylic acid compounds (C) and (C ′) of the present invention have excellent affinity for pigments, that is, good dispersibility due to dispersibility. It progresses and the pigment concentration can be increased. In addition, a composition that requires development is suitable because the dispersion is in a more favorable state, so that good patterning characteristics are exhibited, and there are few development residues in the development and dissolution area.

  Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.

  In the present invention, the molding material refers to an uncured composition put into a mold, or an object is molded by pressing the mold, and then a curing reaction is caused by active energy rays to form, or an uncured composition. It refers to a material used for applications in which a focused light such as a laser is irradiated to cause a curing reaction to be molded.

  Specific applications include a flat sheet, a sealing material to protect the element, a nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, and Particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of the substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, a film-forming material is temporarily applied to a peelable substrate to form a film, and then a so-called dry film in which a film is formed by being bonded to the originally intended substrate also corresponds to the film-forming material. .

  The carboxy group of the reactive polycarboxylic acid compound (C) and / or (C ′) enhances the adhesion to the substrate. Furthermore, since the reactive polycarboxylic acid compound (C) and / or (C ′) is soluble in an alkaline aqueous solution, the composition of the present invention containing the reactive polycarboxylic acid compound (C) and / or (C ′). The product is also preferable as an alkaline water developable resist material composition for coating a plastic substrate or a metal substrate.

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.

  The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful for solder resist materials, interlayer insulating materials for build-up methods, and optical waveguides. It is also used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.

  Particularly suitable applications are the use of permanent resists such as solder resists by taking advantage of the property that a tough cured product can be obtained, and the use of characteristics such as good pigment dispersibility, and printing inks, color filters, etc. It is a resist, particularly a black matrix resist.

  The active energy ray-curable resin composition of the present invention is also used for dry film applications that require mechanical strength before a curing reaction with energy rays. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (A) used in the present invention is in a specific range, the reactive carboxylate compound (B) and / or (B ′) of the present invention is relatively high. Despite its molecular weight, it exhibits good developability.

  There are no particular restrictions on the method for forming the film, 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, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with active energy rays.

  In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various applications, other components can be added to the resin composition with an upper limit of 70% by mass. Examples of other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability. 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-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) 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, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine-based initiator, borate-based initiator, And other photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). Triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide), etc. Gerare, the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  Other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (such as Trigonal PI manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl). ) Ethanone (Sandoz 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.) and the like. Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s -Triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-F Ruechiriden) -4,6-bis (manufactured by trichloromethyl) -s-triazine (Sanwa Chemical Co., Ltd.).

  Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye, and other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurokin Kasei), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [η-5-2-4- (cyclopentadecyl) (1,2 , 3,4,5,6, η)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (such as Irgacure 261 manufactured by Ciba Geigy), bis (y5-cycl Pentadienyl) bis [2,6-difluoro-3-(1H-pyr-1-yl) phenyl] titanium (such as Ciba Geigy Corp. CGI-784), and the like.

  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. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation An inhibitor or the like can be used.

  As other pigment materials, for example, those not intended for coloring, so-called extender pigments can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the resin composition in a range of up to 40% by mass.

  In particular, when a reactive polycarboxylic acid compound (C) or (C ′) is to be used for solder resist applications, a known general epoxy resin may be used as a resin that does not show reactivity to active energy rays. preferable. This is because the carboxy group derived from (C) or (C ′) remains after reaction and curing by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. By using an epoxy resin, the remaining carboxy group is further carboxylated to form a stronger crosslinked structure.

  Further, depending on the purpose of use, a volatile solvent may be added to the resin composition in a range of 50% by mass, more preferably up to 35% by mass.

  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.

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JISK-7236: 2001.
2) Hydroxyl equivalent: measured by a method according to JIS K 0070: 1992 after reacting an epoxy equivalent of the corresponding epoxy resin with an epoxy group in the epoxy resin and an equivalent amount of acetic acid to open the epoxy group. It calculated from the obtained hydroxyl equivalent.
3) Softening point: measured by a method according to JISK-7234: 1986 4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1: Synthesis of Compound (b) Having Two or More Phenolic Hydroxyl Groups in One Molecule A flask equipped with a thermometer, a condenser tube, and a stirrer was charged with 316 parts of phenol and 158 parts of resorcin, and heated to 100 ° C After raising the temperature, 201 parts of 4,4′-bischloromethylbiphenyl was added in portions over 2 hours, and the mixture was further reacted at the same temperature for 5 hours. Thereafter, the temperature was raised to 160 ° C. and all 4,4′-bischloromethylbiphenyl was reacted. Meanwhile, HCl formed was distilled off by trapping with alkali. After completion of the reaction, 266 parts of phenol / resorcin aralkyl resin (b-1) was obtained by distilling off the unreacted phenol and unreacted resorcin under reduced pressure at 180 ° C. using a rotary evaporator. The obtained phenol / resorcin aralkyl resin (b-1) had a hydroxyl group equivalent of 135 g / eq. The softening point was 94 ° C., the ICI viscosity was 470 mPa · s, and the dihydric phenol introduction ratio was 64%.

Example 1 Synthesis of Epoxy Resin (A) A phenol-biphenyl novolac type epoxy resin as the epoxy resin (a) of the above formula (1) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirrer (Nippon Kayaku Co., Ltd. NC-3500; epoxy equivalent 207 g / eq., Softening point 70 ° C.), phenol / resorcinaralkyl resin (b-1) obtained in Synthesis Example 1 (hydroxyl equivalent 135 g / eq., The compound represented by the formula (4) was charged in the amount shown in Table 1, and methyl isobutyl ketone (MIBK) was charged as a solvent so that the solid content was 60 parts by mass. After uniformly dissolving at 70 ° C., 0.5 g of triphenylphosphine was added and stirred at 100 ° C. for 20 hours. After completion of the reaction, oxygen purge was performed to oxidize triphenylphosphine to obtain an epoxy resin (A) resin solution.

  Furthermore, the solvent was removed from the obtained resin solution by drying under reduced pressure to obtain an epoxy resin (A). The epoxy equivalent, hydroxyl equivalent, and softening point (sp) were measured and listed in Table 1.

note)
WPE: Epoxy equivalent (g / eq)
sp: Softening point (° C)
Mol ratio: The molar ratio of the hydroxyl group with respect to the epoxy group of NC-3500 of the synthesis example 1 and GPH-65 is shown.
Comparative Example 1-1 showed the data of NC-3500 itself.

Example 2: Preparation of carboxylate compounds (B) and (B ') The epoxy resin (A) prepared in Example 1, Comparative Example 1-1 (NC-3500 itself) and Comparative Example 1-3 is described in the table. Amount of acrylic acid (abbreviation AA, Mw = 72) as a compound (c) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule, Metallic propionic acid (abbreviation: DMPA, Mw = 134) triphenylphosphine (3 g) as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent to a solid content of 80%, reacted at 100 ° C. for 24 hours, reactive carboxylate Compound (B) and (B ′) solutions were obtained.

注）ＡＡのエポキシ樹脂（Ａ）に対するモル比はいずれも１．０である。

Note) The molar ratio of AA to the epoxy resin (A) is 1.0.

Example 3: Preparation of reactive polycarboxylic acid compounds (C) and (C ')
Table 3 shows tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride (e) to 299 g of the solutions of the reactive carboxylate compounds (B) and (B ′) obtained in Example 2 and Comparative Example 2. Propylene glycol monomethyl ether monoacetate is added in an amount and a solid content of 65 parts by mass as a solvent, and heated to 100 ° C. to effect an acid addition reaction to obtain reactive polycarboxylic acid compound (C) and (C ′) solutions It was.

Example 4: Preparation of composition for hard coat 20 g of reactive carboxylate compound (B) / (B ′) synthesized in Example 2 and Comparative Example 2, dipenta as radical curable monomer (D) 4 g of erythritol hexaacrylate and 1.5 g of Irgacure 184 as an ultraviolet reaction initiator were mixed and dissolved by heating.
Further, this was coated on a polycarbonate plate by a hand applicator so as to have a film thickness of 20 μm at the time of drying, and the solvent was dried in an electric oven at 80 ° C. for 30 minutes. After drying, an ultraviolet ray vertical exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp was irradiated and cured with an ultraviolet ray with an irradiation dose of 1000 mJ to obtain an article overcoated with a resin composition.
The hardness of the coating film of the article overcoated with this resin composition was measured according to JIS K5600-5-4: 1999, and an impact resistance test was conducted according to ISO6272-1: 2002.
Impact resistance test ○: No scratch or peeling.
Δ: Slightly scratched
X: It peeled off.

  As is apparent from the above results, the example and the impact resistance were improved as compared with the comparative example.

Example 5: Preparation of dry film type resist composition
56.73 g of the reactive polycarboxylic acid compound (C) obtained in Example 3 and Comparative Example 3, and DPCA-60 (trade name: Nippon Kayaku Co., Ltd., polyfunctional acrylate as the other reactive compound (D) Monomer) 5.67 g, 2.92 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as photopolymerization initiator and 0.58 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), NC- Add 17.54 g of 3000H (Nippon Kayaku Co., Ltd.), 0.73 g of melamine as a thermosetting catalyst and 5.67 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent, and knead and uniformly disperse in a bead mill. A resist resin composition was obtained. The obtained composition was uniformly applied to a polyethylene terephthalate film serving as a support film using a wire bar coater # 20, and passed through a hot air drying furnace at a temperature of 70 ° C. to form a resin layer having a thickness of 20 μm. A polyethylene film serving as a protective film was pasted on the resin layer to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

Next, in order to estimate the mask on which the circuit pattern was drawn and sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays of 500 mJ / cm ² . Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film.

<Sensitivity evaluation>
Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).

<Developability evaluation>
The developability was evaluated based on the time until the pattern shape portion was completely developed, that is, the so-called break time when developing the exposed portion that passed through the pattern mask (unit: second).

<Curability evaluation>
The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C.
The evaluation method was based on JIS K5600-5-4: 1999.

<Folding resistance evaluation>
The polyimide printed circuit board on which the cured film of the resist was formed was folded in a mountain with the cured film side up, and the bent part was rubbed with fingers. The bent portion was returned to its original position, and the resist film was observed with a magnifying glass.
○: No crack Δ: Slight crack is observed ×: Peel

  As is clear from the above results, the resin composition of the present invention has high hardness and high folding resistance. Also, it has good developability and sensitivity as a resist.

Example 6: Evaluation of flame retardancy Mixing and stirring 10.0 g of the resist composition prepared in Example 5 and Comparative Example 5 and 0.5 g of a phosphorus-based reactive flame retardant (FRM-1000 manufactured by Nippon Kayaku Co., Ltd.) Then, a curable resin composition was obtained. The composition was applied to a polyimide film having a film thickness of 25 μm with a wire bar coater # 20 and passed through a hot air drying furnace at a temperature of 70 ° C. to form a resin layer having a thickness of approximately 15 μm. An ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW) was used to irradiate with 500 mJ / cm ² of ultraviolet rays. After irradiation, the printed circuit board was subjected to a heat curing reaction in a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film. The obtained cured film was cut out together with the polyimide base film in a strip shape having a length of 20 cm and a width of 2 cm. The cut out film was suspended vertically and lit by a lighter from the lower end to evaluate flame retardancy. The results are shown in Table 6.
Flame retardant evaluation ○: Ignites but extinguishes before burning.
X: Completely burned.

  From the above results, it became clear that the reactive polycarboxylic acid compounds (C) and (C ′) of the present invention are flame retardant materials.

Example 7: Evaluation on pigment dispersibility 20 g of the reactive polycarboxylic acid compounds (C) and (C ′) obtained in Example 3 and Comparative Example 3, and DPHA (trade name: product name) as the other reactive compound (D) Nippon Kayaku Co., Ltd. acrylate monomer) 5.0g, propylene glycol monomethyl ether acetate 10g as an organic solvent, and Mitsubishi carbon black MA-100: 10g as a color pigment were mixed and stirred. 35 g of glass beads were put therein and dispersed for 1 hour with a paint shaker.
The dispersion after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried for 10 minutes with a hot air dryer at 80 ° C.
The gloss of the coating film surface after drying was measured using a 60 ° reflection gloss meter to evaluate the dispersibility of the carbon black. Table 7 shows the results. The higher the gloss value, the better the pigment dispersibility.

  The resin composition of the present invention is suitable as a material having both curability, flexibility, toughness, and flame retardancy, and as a hard coat material and a resist material requiring flexibility capable of alkali development. In particular, active energy ray-curable printing inks and color resists are suitable for color resists for LCDs, black matrices, and the like as materials having both resist dispersibility and pigment suitability such as developability.

Claims (11)

An epoxy resin (A) obtained by reacting an epoxy resin (a) represented by the following general formula (1) with a compound (b) having two or more phenolic hydroxyl groups in one molecule.

In general formula (1), Ar is each independently either (2) or (3), and the molar ratio of (2) and (3) is (2) / (3) = 1-3. . n is the number of repetitions, and is a positive number from 0 to 5. Ar may be the same or different. G is a glycidyl group. A reactive epoxycarboxylate compound obtained by reacting the epoxy resin (A) according to claim 1 with a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule. (B). The epoxy resin (A) according to claim 1, a compound (c) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in the molecule, and a compound having both a hydroxyl group and a carboxy group in one molecule ( A reactive epoxycarboxylate compound (B ′) obtained by reacting with d). A reactive polycarboxylic acid compound (C) obtained by reacting the carboxylate compound (B) according to claim 2 with a polybasic acid anhydride (e). An active energy ray-curable resin composition comprising the carboxylate compound (B) according to claim 2 and / or the reactive polycarboxylic acid compound (C) according to claim 4. The active energy ray-curable resin composition according to claim 4, further comprising a reactive compound (D). A reactive polycarboxylic acid compound (C ') obtained by reacting the carboxylate compound (B') according to claim 3 with a polybasic acid anhydride (e). An active energy ray-curable resin composition comprising the carboxylate compound (B ') according to claim 3 and / or the reactive polycarboxylic acid compound (C') according to claim 7. The active energy ray-curable resin composition according to claim 8, further comprising a reactive compound (D). A cured product of the active energy ray-curable resin composition according to any one of claims 4 to 10. An article having the cured product according to claim 10.