Reactive polycarboxylic acid compound, active energy beam curable resin composition using the same, and the cured product thereof

Abstract

The present invention aims to provide an active energy beam curable resin composition capable of patterning by photolithography and having a low outgassing amount, and a cured product thereof. The present invention was reached by discovering that a resin composition utilizing a reaction product of a specific epoxy resin, an unsaturated group-containing carboxylic acid, and a specific polybasic acid anhydride solves the above problem.

Description

Technology Field

[0001] The present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy beam curable resin composition containing the same, and a cured product thereof. In particular, the invention relates to a novel reactive polycarboxylic acid compound suitable as a resist material applicable as a material for display devices such as organic EL display elements, an active energy beam curable resin composition containing the same, and a cured product thereof. Background Technology

[0002] Organic EL display devices utilizing the electric field emission of organic compounds have many features, such as being self-emissive, having no dependence on the viewing angle, having a fast response speed, and being thin and lightweight, so active development is being carried out for use in image display devices.

[0003] Pattern forming technology by photolithography is used for the fabrication of components of display devices such as organic EL displays, such as partitions or flattening layers, and active energy beam curable resin compositions are used. Prior art literature

[0004] International Publication No. 2018 / 101314 The problem to be solved

[0005] Recently, there has been a problem where outgassing from active energy beam curable resin materials contaminates devices or manufacturing equipment, so there is a demand for the development of active energy beam curable resin materials with low outgassing. Therefore, the present invention aims to provide an active energy beam curable resin composition and a cured product thereof that are capable of patterning by photolithography and have low outgassing. More specifically, the invention aims to provide an active energy beam curable resin material with low outgassing of acid sugars. means of solving the problem

[0006] In order to solve the above problem, the inventors conducted a thorough examination and discovered that a resin and a resin composition utilizing a reaction product of a specific epoxy resin, an unsaturated group-containing carboxylic acid, and a specific polybasic acid anhydride solve the above problem, thereby arriving at the present invention.

[0007] That is, the present invention is,

[0008] [1] A reactive polycarboxylic acid compound (A) obtained by reacting a reactive epoxycarboxylate compound (c), which is obtained by reacting a carboxylic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule with an epoxy resin (a) represented by the following formula (1) or (2), with a polybasic acid anhydride (d) represented by the following formula (3).

[0009]

[0010] (In the formula, n represents the mean value and is a number from 0 to 10. G represents a glycidyl group.)

[0011]

[0012] (In the formula, n represents an average value and is a number from 0 to 10. P and R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and multiple P and R may be identical or different from each other. G represents a glycidyl group.)

[0013]

[0014] (In Equation (3), R1 independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. m represents an integer from 1 to 3.)

[0015] [2] An active energy beam curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1].

[0016] [3] An active energy beam curable resin composition described in [2] comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A) above.

[0017] [4] Active energy beam curable resin composition described in [2] or [3] containing a photopolymerization initiator.

[0018] [5] An active energy beam curing resin composition described in any one of [2] to [4], which is a material for display devices.

[0019] [6] A cured product of an active energy beam curing resin composition as described in any one of [2] to [5]. Effects of the invention

[0020] The active energy beam curable resin composition comprising the reactive polycarboxylic acid compound (A) of the present invention can provide a resin cured product having excellent developability, capable of patterning by photolithography, and having a low outgassing amount. Specific details for implementing the invention

[0021] (Form for carrying out the invention)

[0022] The present invention will be described in detail below.

[0023] The reactive polycarboxylic acid compound (A) of the present invention is obtained by reacting an epoxy resin (a) having a structure represented by the following formula (1) or (2) with a carboxylic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule to obtain a reactive epoxycarboxylate compound (c). Subsequently, it can be obtained by reacting a polybasic acid anhydride (d) represented by the following formula (3).

[0024]

[0025] In the above formula (1), n ​​represents the average value and represents a number from 0 to 10.

[0026] G represents a glycidyl group.

[0027]

[0028] In the above formula (2), n represents the average value and represents a number from 0 to 10.

[0029] P and R each independently represent any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and the plurality of P and R may be the same or different from each other. As an alkyl group having 1 to 8 carbon atoms, it may be any straight-chain, branched, or cyclic alkyl group, and specifically, methyl group, cyclohexylmethyl group, ethyl group, 2-cyclopentylethyl group, propyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-butyl group, 3-methylbutane-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 2-pentyl group, 2-methylpentane-2-yl group, 4,4-dimethylpentane-2-yl group, 3-pentyl group, 3-ethylpentane-3-yl group, cyclopentyl group, Examples include 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexane-2-yl group, 5,5-dimethylhexane-2-yl group, 3-hexyl group, 2,4-dimethylhexane-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group or bicyclo[2.2.2]octyl group, etc. Examples of the above aryl groups include phenyl groups, o-xyl groups, m-xyl groups, p-xyl groups, 2,3-xyl groups, 2,4-xyl groups, 2,5-xyl groups, 2,6-xyl groups, 3,5-xyl groups, naphthyl groups, anthyl groups, etc. It is preferable that P and R are hydrogen atoms.

[0030] G represents the glycidyl group.)

[0031]

[0032] In the above formula (3), R1 each independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. The above alkyl group having 1 to 10 carbon atoms may be any straight-chain, branched, or cyclic alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 1-(1,1-dimethylethyl) group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 1,2-dimethylbutyl group, 1-ethylpropyl group, cyclopentyl group, 5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, Examples include 2,6-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, bicyclo[2.2.1]heptane-2-yl group, bicyclo[2.2.2]octane-2-yl group, adamantan-2-yl group, bicyclo[2.2.1]heptane-2-yl group, adamantan-1-yl group, etc. R1 is preferably hydrogen. m represents an integer from 1 to 3.

[0033] First, a carboxylation process is described to obtain a reactive epoxycarboxylate compound (c) by imparting reactivity to a carboxylate compound.

[0034] The epoxy resin (a) used in the present invention is an epoxy resin represented by the above formula (1) or (2). The epoxy resin represented by the above formula (1) is generally available under various trade names, such as EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 manufactured by Nippon Kayaku Co., Ltd., Epiclone N-660, Epiclone N-665, Epiclone N-670, Epiclone N-673, Epiclone N-680, Epiclone N-690, Epiclone N-695, Epiclone N-665-EXP, Epiclone N-672-EXP manufactured by DIC Co., Ltd., and YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A manufactured by Nittetsu Chemical & Material Co., Ltd.

[0035] The epoxy resin represented by the above formula (2) is generally available under various trade names, such as NC-3000, NC-3100, NC-3000-L, NC-3000-H, NC-3000-LC, NC-3000-LLC manufactured by Nippon Kayaku Co., Ltd.

[0036] In the present invention, a carboxylic acid compound (b) (hereinafter also simply referred to as “carboxylic acid compound (b)”) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule is reacted to impart reactivity to an active energy line. There is no limitation as long as there is at least one ethylenically unsaturated group and a carboxyl group in the molecule.

[0037] Examples of carboxylic acid compounds (b) that have both an ethylenically unsaturated group and a carboxyl group capable of polymerization in one molecule include (meth)acrylic acids, crotonic acid, α-cyanosinnamic acid, cinnamic acid, or reaction products of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group. In the above, as (meth)acrylic acids, for example, (meth)acrylic acid, β-styrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimers, semi-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid anhydride with a (meth)acrylate derivative having one hydroxyl group in one molecule, and semi-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid with a monoglycidyl (meth)acrylate derivative, and monocarboxylic acid compounds containing one carboxyl group in one molecule, additionally, semi-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid anhydride with a (meth)acrylate derivative having multiple hydroxyl groups in one molecule, and equimolar reactions of a saturated or unsaturated dibasic acid with a glycidyl (meth)acrylate derivative having multiple epoxy groups Examples of reactants include polycarboxylic acid compounds having multiple carboxyl groups in one molecule, such as antiesters. Among these, (meth)acrylic acid is preferred.

[0038] Among these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), it is preferable that the carboxylic acid compound (b) be a monocarboxylic acid, and even when monocarboxylic acid and polycarboxylic acid are used together, it is preferable that the value expressed as the molar amount of monocarboxylic acid / molar amount of polycarboxylic acid be 15 or higher.

[0039] Most preferably, (meth)acrylic acid, the reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid can be cited in terms of sensitivity when used as an active energy beam curable resin composition.

[0040] The input ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this carboxylation reaction must be appropriately adjusted according to the application. That is, when all epoxy groups are carboxylated, no unreacted epoxy groups remain, so the storage stability as a reactive epoxycarboxylate compound (c) is high. In this case, only the reactivity due to the introduced double bond is utilized.

[0041] Meanwhile, by reducing the amount of carboxylic acid compound (b) to leave unreacted residual epoxy groups, it is possible to utilize a combination of the reactivity of the introduced unsaturated bonds and the reaction of the residual epoxy groups, such as polymerization by a photocation catalyst or thermal polymerization. However, in this case, care must be taken in examining the storage and manufacturing conditions of the reactive epoxycarboxylate compound (c).

[0042] When preparing a reactive epoxycarboxylate compound (c) that does not leave any residual epoxy groups, it is preferable that the total amount of the carboxylic acid compound (b) be 90 to 120 equivalents per 1 equivalent of the epoxy resin (a). Within this range, it is possible to produce it under relatively stable conditions. If the amount of carboxylic acid compound added is greater than this, it is not desirable because an excess of the carboxylic acid compound (b) and the reactive epoxycarboxylate compound (c) will remain.

[0043] In addition, when epoxy groups are retained, it is preferable that the total amount of carboxylic acid compounds (b) be 20 to 90 equivalents per 1 equivalent of epoxy resin (a). If this range is exceeded, the effect of composite curing is weakened. Of course, in this case, sufficient attention must be paid to gelation during the reaction and the stability of the reactive epoxycarboxylate compounds (c) over time.

[0044] The carboxylation reaction may be carried out in a solvent-free manner or diluted with a solvent. As for the solvent that can be used here, there are no particular limitations as long as it is an inert solvent for the carboxylation reaction.

[0045] The amount of solvent used should be appropriately adjusted according to the viscosity or application of the resin obtained, but preferably, it is used to have a solid content of 90 to 20 mass%, more preferably 80 to 30 mass%.

[0046] Specifically, examples include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and mixtures thereof such as petroleum ether, white gasoline, and solvent naphtha, as well as ester solvents, ether solvents, and ketone solvents.

[0047] Examples of ester-based solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipicate.

[0048] Examples of ether-based solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

[0049] Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0050] In addition, the process may be carried out in a single or mixed organic solvent, such as a reactive compound (B) (hereinafter also simply referred to as "reactive compound (B)") other than the reactive polycarboxylic acid compound (A) described below. In this case, when used as a curable resin composition, it is preferable because it can be used directly as a composition.

[0051] During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of said catalyst used is 0.1 to 10 parts by mass per 100 parts by mass of the total amount of reactants, namely epoxy resin (a), carboxylic acid compound (b), and optionally a solvent and others. 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 known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, chromium octanoate, zirconium octanoate, etc.

[0052] In addition, a thermal polymerization inhibitor may be used. As a thermal polymerization inhibitor, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc.

[0053] The carboxylation reaction is appropriately sampled, and the point at which the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less, is the endpoint.

[0054] The preferred molecular weight range of the reactive epoxycarboxylate compound (d) obtained in this way is a polystyrene-equivalent weight average molecular weight in GPC in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. When the polystyrene-equivalent weight average molecular weight in GPC is in the range of 500 to 50,000, the toughness of the cured product can be sufficiently exhibited, and the coating properties also become good.

[0055] If the molecular weight is smaller than this, the toughness of the cured product is not fully exhibited, and if it is excessively larger, the viscosity increases, making coating and the like difficult.

[0056] Next, the acid addition process (hereinafter also simply referred to as the “acid addition reaction”) will be described in detail. The acid addition process is performed with the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxyl group as needed into the reactive epoxycarboxylate compound (c) obtained in the previous process. That is, a carboxyl group is introduced through an ester bond by adding a polybasic acid anhydride (d) represented by formula (2) above (hereinafter also simply referred to as the “polybasic acid anhydride (d)”) to the hydroxyl group generated by the carboxylation reaction.

[0057] Examples of alkyl groups having 1 to 10 carbon atoms in the above formula (2) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. In the above formula (2), R1 is preferably a hydrogen atom or a methyl group.

[0058] As the above polybasic acid anhydride (d), a compound represented by the following formula (3) is preferred.

[0059]

[0060] The reaction for adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added should be appropriately changed depending on the application.

[0061] For example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkaline aqueous solution developing type resist material, it is preferable to add a calculated value such that the solid dispersion acid value (based on JISK 5601-2-1: 1999) of the reactive polycarboxylic acid compound (A) obtained finally is preferably 10 to 110 mgKOH / g, and more preferably 20 to 100 mgKOH / g. When the solid dispersion acid value is within this range, the alkaline aqueous solution developing properties of the active energy beam curing resin composition of the present invention exhibit good developing properties. That is, good patterning properties and a wide control range for overdevelopment are available, and there is no excess acid anhydride remaining.

[0062] During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of said catalyst used is 0.1 to 10 parts by mass relative to the total amount of reactants, namely the epoxy carboxylate compound (c) obtained from the epoxy compound (a) and the carboxylic acid compound (b), and polybasic acid anhydride (d), and optionally a solvent and others. 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 instance, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, chromium octanoate, zirconium octanoate, etc.

[0063] The acid addition reaction may be carried out without a solvent or by diluting with a solvent. There are no particular limitations on the solvents that can be used here, as long as they are inert solvents for the acid addition reaction. Furthermore, if a solvent was used in the preceding carboxylation reaction, the product may be directly provided that it is inert for both reactions, and thus provided that it is directly supplied to the next acid addition reaction without removing the solvent. The solvents that can be used should be the same as those used in the carboxylation reaction.

[0064] The amount of solvent used should be appropriately adjusted according to the viscosity or application of the resin obtained, but preferably 70 to 30 mass%, more preferably 60 to 40 mass% with respect to the solid content.

[0065] In addition, the above-mentioned reactive compound (B) may be used alone or in a mixed organic solvent. In this case, when used as a curable resin composition, it is preferable because it can be used directly as a composition.

[0066] In addition, it is preferable to use thermal polymerization inhibitors, etc., that are the same as those exemplified in the above carboxylation reaction.

[0067] This acid addition reaction is appropriately sampled, and the point at which the acid value of the reactant becomes within the range of plus or minus 10% of the set acid value is the endpoint.

[0068] The preferred molecular weight range of the reactive polycarboxylic acid compound (A) obtained in this way is a polystyrene equivalent weight average molecular weight in GPC (gel permeation chromatography) measurement in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

[0069] If the molecular weight is smaller than this, the toughness of the cured product is not fully exhibited, and if it is excessively larger, the viscosity increases, making coating and the like difficult.

[0070] Specific examples of reactive compounds (B) that can be used in the present invention include so-called reactive oligomers such as radical reactive acrylates, cationic reactive other epoxy compounds, and vinyl compounds that respond to both of the same.

[0071] Examples of acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, epoxy acrylates, polyester acrylates, urethane acrylates, etc.

[0072] Examples of 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, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.

[0073] As polyfunctional (meth)acrylates, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene 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, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of the ε-caprolactone adduct of hydroxybivalsan neophenglycol, dipentaerythritol and Examples of reactants of ε-caprolactone include poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, 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 and its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate and its ethylene oxide adduct, etc.

[0074] 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, ethylene glycol divinyl ether, etc. Examples of styrenes include styrene, methyl styrene, ethyl styrene, etc. Examples of other vinyl compounds include triallyl isocyanurate, trimetallyl isocyanurate, etc.

[0075] In addition, so-called reactive oligomers include urethane acrylates that combine a functional group responsive to active energy rays and a urethane bond within the same molecule, polyester acrylates that likewise combine a functional group responsive to active energy rays and an ester bond within the same molecule, epoxy acrylates derived from epoxy resins that combine a functional group responsive to active energy rays within the same molecule, and reactive oligomers in which these bonds are utilized in combination.

[0076] In addition, as for the cationic reactive monomer, there are generally no specific limitations as long as it is a compound having an epoxy group. For example, glycidyl (meth)acrylate, methylglycidyl ether, ethylglycidyl ether, butylglycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide, "Cyracure UVR-6110", etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (manufactured by Union Carbide, "ELR-4206", etc.), limonene dioxide (manufactured by Daicel Kagaku Kogyo, "Celoxide 3000", etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, Examples include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (Union Carbide's "Cyracure UVR-6128", etc.), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, etc.

[0077] Among these, radical-curing acrylates are most preferred as the reactive compound (B). In the case of cationic types, the carboxylic acid and the epoxy group react, so it becomes necessary to make it a two-component mixed type.

[0078] The active energy beam curable resin composition of the present invention can be obtained by mixing the reactive polycarboxylic acid compound (A) of the present invention with other reactive compounds (B). At this time, other components may be added appropriately depending on the application.

[0079] The active energy beam curable resin composition of the present invention comprises 97 to 5 parts by mass, preferably 87 to 10 parts by mass, of a reactive polycarboxylic acid compound (A) and 3 to 95 parts by mass, preferably 3 to 90 parts by mass, of other reactive compounds (B). If necessary, it may also comprise 0 to 80 parts by mass of other components.

[0080] In addition, other components may be added to the composition, up to a maximum of 70 parts by mass, for the purpose of making the active energy beam curable resin composition of the present invention suitable for various applications. Examples of other components include photopolymerization initiators, other additives, coloring materials, thermosetting catalysts, or volatile solvents added for viscosity adjustment to impart coating suitability.

[0081] The active energy beam curable resin composition of the present invention may additionally include a photopolymerization initiator. As the photopolymerization initiator, a radical-type photopolymerization initiator and a cationic-type photopolymerization initiator are preferred.

[0082] As radical-type photopolymerization initiators, examples include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin sobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxantone, 2-isopropylthioxantone, Examples of known general radical-type photopolymerization initiators include thioxantones such as 2-chlorothioxantone; ketal types such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0083] In addition, cationic photopolymerization initiators include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine-based initiators, borate-based initiators, and other photoacid generators.

[0084] Examples of Lewis acid diazonium salts include p-methoxyphenyldiazonium fluorophosphonate, N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Kagaku Kogyo Co., Ltd.), etc. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, etc. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by UnionCarbide Co., Ltd.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by UnionCarbide Co., Ltd.), etc. Examples of Lewis acid phosphonium salts include triphenylphosphonium hexafluoroantimonate, etc.

[0085] Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanolone (TrigonalPI manufactured by AKZO, etc.), 2,2-dichloro-1-4-(phenoxyphenyl)ethanolone (Sandray 1000 manufactured by Sandoz, etc.), α,α,α-tribromomethylphenylsulfone (BMPS manufactured by Seitetsu Kagaku, etc.). As triazine-based initiators, 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (Triazine A manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (Triazine PMS manufactured by Panchim, etc.), 2,4-trichloromethyl-(piperonyl)-6-triazine (Triazine PP manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B manufactured by Panchim, etc.), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical, etc.), Examples include 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemicals).

[0086] Examples of borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Nippon Kanko Shikiso, and other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurogane Kasei Co., Ltd., etc.), 2,2-azobis(2-amino-propane)dihydrochloride (V50 manufactured by Waco Sunyaku Co., Ltd., etc.), 2,2-azobis[2-(imidazoline-2yl)propane]dihydrochloride (VA044 manufactured by Waco Sunyaku Co., Ltd., etc.), [eta-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6, Examples include [eta]-(methylethyl)-benzene]iron(II)hexafluorophosphonate (Irgacure261 manufactured by CibaGeigy, etc.), bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridine-1-yl)phenyl]titanium (CGI-784 manufactured by CibaGeigy, etc.).

[0087] In addition, azo-based initiators such as azobis-isobutyronitrile, heat-sensitive peroxide-based radical initiators such as benzoyl peroxide, etc. may be used together. Furthermore, both radical and cationic photopolymerization initiators may be used together. One type of photopolymerization initiator may be used alone, or two or more types may be used together.

[0088] Among these, considering the characteristics of the reactive polycarboxylic acid compound (A) of the present invention, a radical-type photopolymerization initiator is particularly preferred.

[0089] In addition, the active energy beam curable resin composition of the present invention may include a coloring pigment. As a coloring pigment, for example, a so-called extender pigment that is not intended for coloring may be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, carbon black, etc.

[0090] In addition, the active energy beam curable resin composition of the present invention may include other additives as needed. Examples of other additives may include a thermosetting catalyst such as melamine, a thixotropy impregnating agent such as Aerosil, a silicone-based or fluorine-based leveling agent or defoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, etc.

[0091] In addition, resins that do not exhibit reactivity to active energy rays (so-called inert polymers) may be used, for example, other epoxy resins, phenolic 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 modifications thereof. It is preferable to use these in a range of up to 40 parts by mass in the resin composition.

[0092] In particular, when using a reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not exhibit reactivity to active energy rays. This is because carboxyl groups originating from the reactive polycarboxylic acid compound (A) remain even after reaction and curing by active energy rays, and consequently, the cured product has poor water resistance and hydrolytic properties. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated to form a more robust cross-linked structure. The known general epoxy resin may utilize the above-mentioned cationic reactive monomer.

[0093] In addition, depending on the intended use, a volatile solvent may be added to the resin composition in an amount of 50 parts by mass, more preferably up to 35 parts by mass, for the purpose of adjusting viscosity.

[0094] The active energy beam-curing resin composition of the present invention is easily cured by active energy beams. Specific examples of active energy beams include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and laser beams, and particle beams such as alpha rays, beta rays, and electron beams. Considering the suitable applications of the present invention, among these, ultraviolet rays, laser beams, visible light, or electron beams are preferred.

[0095] In the present invention, the material for the display device is a material used in display elements such as liquid crystal display devices, organic EL devices, and electronic paper. Specific applications include spacers, protective films, planarization films, interlayer insulating films, and barrier materials. Among these, the display device according to one embodiment of the present invention is preferably an organic EL device.

[0096] The present invention includes a cured product obtained by irradiating an active energy beam onto the above-mentioned curable resin composition, and also includes a multilayer material having a layer of said cured product.

[0097] Furthermore, it is also desirable to utilize the unreacted reactive polycarboxylic acid compound (A) as an alkaline water developing type resist material composition by taking advantage of the characteristic that it becomes soluble in an alkaline aqueous solution.

[0098] In the present invention, the term "resist material composition" refers to an active energy-ray responsive composition intended to perform a drawing by utilizing the difference in physical properties between the irradiated and unirradiated portions, wherein a film layer of the composition is formed on a substrate, and then active energy rays, such as ultraviolet rays, are partially irradiated. Specifically, it is a composition used for the purpose of performing a drawing by removing the irradiated or unirradiated portions by some method, such as dissolving them in a solvent or an alkaline solution.

[0099] The active energy beam curable resin composition, which is the resist material composition of the present invention, can be adapted to various patternable materials, and is particularly useful, for example, as a solder resist material and an interlayer insulating material for a build-up method, and furthermore, is used as an optical waveguide in electrical, electronic, and optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates.

[0100] Particularly suitable applications include utilizing properties such as good heat resistance and developability to widely use the resin composition in applications where it is required, such as photosensitive films, photosensitive films attached to supports, insulating resin sheets such as prepregs, circuit boards (for laminated boards, multilayer printed circuit boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, color resists, color filters, black matrices, etc.

[0101] In addition, it can be suitably used for resin compositions for insulating layers of multilayer printed circuit boards (multilayer printed circuit boards in which a cured product of a photosensitive resin composition is used as an insulating layer), resin compositions for interlayer insulating layers (multilayer printed circuit boards in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer), resin compositions for forming plating (multilayer printed circuit boards in which plating is formed on a cured product of a photosensitive resin composition), etc.

[0102] Patterning using the active energy beam curable resin composition of the present invention can be performed, for example, as follows. A curable resin composition of the present invention can be applied to a substrate with a film thickness of 0.1 to 200 μm by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating, and a coating film can be formed by drying the film at a temperature of typically 50 to 110°C, preferably 60 to 100°C. After that, high-energy rays such as ultraviolet rays are irradiated directly or indirectly onto the coating film through a photomask having an exposure pattern formed thereon at an intensity of typically 10 to 2000 mJ / cm², and a desired pattern can be obtained by, for example, spraying, vibrating immersion, paddle, brushing, etc., using a developer described later.

[0103] As the alkaline aqueous solution used for the above phenomenon, inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate, or organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine may be used. This aqueous solution may additionally contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0104] In addition, it is particularly suitable for use as a dry film requiring mechanical strength prior to the curing reaction by active energy rays. That is, since the balance of hydroxyl groups and epoxy groups of the epoxy resin (a) used in the present invention is within a specific range, the reactive polycarboxylic acid compound (A) of the present invention can exhibit good developability even though it has a relatively high molecular weight.

[0105] There are no particular restrictions on the method of forming the film, but various coating methods such as intaglio printing methods like gravure, relief printing methods like flexo, screen printing methods like silk screen, flatbed printing methods like offset, roll coater, knife coater, die coater, curtain coater, and spin coater may be arbitrarily adopted.

[0106] The term "cured product of the active energy beam curable resin composition of the present invention" refers to a product that is cured by irradiating the active energy beam curable resin composition of the present invention with an active energy beam.

[0107] Examples

[0108] The present invention will be explained in more detail below by way of examples, but the present invention is not limited by these examples. Also, in the examples, unless specifically stated otherwise, % represents mass %.

[0109] The softening point, epoxy equivalent, and acid value were measured under the following conditions.

[0110] 1) Epoxy equivalent: Measured according to the method of JISK7236:2001.

[0111] 2) Softening point: Measured according to the method of JISK 7234:1986.

[0112] 3) Acid value: Measured according to the method of JISK0070:1992.

[0113] 4) The GPC (Gel Permeation Chromatography) measurement conditions are as follows.

[0114] Model: TOSOH HLC-8220 GPC

[0115] Column: Super HZM-N

[0116] Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C

[0117] Detector: RI (Refractor)

[0118] Molecular weight standard: Polystyrene

[0119] (Synthesization Example 1): Synthesis of reactive epoxycarboxylate compound (c)

[0120] 218 g of cresol novolak-type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., softening point 92°C, epoxy equivalent 218 g / eq.) and 72.0 g of acrylic acid (AA) as a carboxylic acid compound (b) were added. 1.25 g of triphenylphosphine was added as a catalyst and propylene glycol monomethyl ether monoacetate was added as a solvent to achieve a solid content of 70 mass%, and the mixture was reacted at 100°C for 24 hours to obtain a solution of a reactive epoxycarboxylate compound (c).

[0121] (Example 1-1): Preparation of a reactive polycarboxylic acid compound (A-1)

[0122] To 50.0 g of the solution of the reactive epoxycarboxylate compound (c) obtained in Synthesis Example 1, 2.56 g of trimellitic anhydride was added as a polybasic acid anhydride (d), and propylene glycol monomethyl ether monoacetate was added as a solvent to achieve a solid content of 50%, and an acid addition reaction was carried out at 100°C to obtain a solution of the reactive polycarboxylic acid compound (A-1) with a solid-dispersed acid value of 39.5 mg·KOH / g. The solid-dispersed acid value (mg·KOH / g) was measured as a solution and converted to a value in terms of solid content.

[0123] (Comparative Example 1-1): Preparation of a reactive polycarboxylic acid compound (A-2)

[0124] To 50.0 g of the solution of the reactive epoxycarboxylate compound (c) obtained in Synthesis Example 1, 4.11 g of phthalic anhydride as a polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent to achieve a solid content of 50% were added, and an acid addition reaction was carried out at 100°C to obtain a solution of the reactive polycarboxylic acid compound (A-2) with a solid-dispersed acid value of 40.6 mg·KOH / g. The solid-dispersed acid value (mg·KOH / g) was measured as a solution and converted to a value in terms of solid content.

[0125] (Comparative Example 1-2): Preparation of a reactive polycarboxylic acid compound (A-3)

[0126] To 50.0 g of the solution of the reactive epoxycarboxylate compound (c) obtained in Synthesis Example 1, 4.32 g of THPA (1,2,3,6-tetrahydrophthalic anhydride) as a polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent to achieve a solid content of 50% were added, and an acid addition reaction was carried out at 100°C to obtain a solution of the reactive polycarboxylic acid compound (A-3) with a solid-dispersed acid value of 42.2 mg·KOH / g. The solid-dispersed acid value (mg·KOH / g) was measured as a solution and converted to a value in terms of solid content.

[0127] (Synthesization Example 2): Synthesis of reactive epoxycarboxylate compound (c)

[0128] 288 g of NC-3000H (manufactured by Nippon Kayaku Co., Ltd., softening point 92°C, epoxy equivalent 288 g / eq.) and 72.0 g of acrylic acid (AA) as a carboxylic acid compound (b) were added. 1.54 g of triphenylphosphine was added as a catalyst and propylene glycol monomethyl ether monoacetate was added as a solvent to achieve a solid content of 70 mass%, and the mixture was reacted at 100°C for 24 hours to obtain a solution of a reactive epoxycarboxylate compound (c).

[0129] (Examples 1-2): Preparation of a reactive polycarboxylic acid compound (A-4)

[0130] To 50.0 g of the solution of the reactive epoxycarboxylate compound (c) obtained in Synthesis Example 2, 3.98 g of trimellitic anhydride was added as a polybasic acid anhydride (d), and propylene glycol monomethyl ether monoacetate was added as a solvent to achieve a solid content of 50%, and an acid addition reaction was carried out at 100°C to obtain a solution of the reactive polycarboxylic acid compound (A-4) with a solid-dispersed acid value of 61.0 mg·KOH / g. The solid-dispersed acid value (mg·KOH / g) was measured as a solution and converted to a value in terms of solid content.

[0131] (Comparative Example 1-2): Preparation of a reactive polycarboxylic acid compound (A-5)

[0132] To 50.0 g of the solution of the reactive epoxycarboxylate compound (c) obtained in Synthesis Example 2, 6.76 g of THPA (1,2,3,6-tetrahydrophthalic anhydride) as a polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent to achieve a solid content of 50% were added, and an acid addition reaction was carried out at 100°C to obtain a solution of the reactive polycarboxylic acid compound (A-5) with a solid-dispersed acid value of 60.5 mg·KOH / g. The solid-dispersed acid value (mg·KOH / g) was measured as a solution and converted to a value in terms of solid content.

[0133] (Example 3 and Comparative Example 3): Preparation of resin composition, evaluation of developability, and evaluation of outgassing amount

[0134] 2.00 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1-1 and Comparative Example 1-2, 0.67 g of DPHA (product name: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.) as another reactive compound (B), 0.08 g of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, and 1.63 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added and uniformly dispersed to obtain a resin composition.

[0135] Each item of the evaluation criteria is described in detail.

[0136] Phenomenon Assessment (Abbreviation in table: Phenomenon)

[0137] After applying the resin composition onto a glass substrate using a spin coater, it was dried for 5 minutes in a hot air dryer at 80°C. Then, spray development was performed with a 1% sodium carbonate aqueous solution (spray pressure 0.2 MPa), and the developability was evaluated based on the time until the coating film completely dissolved, known as the break time (unit: seconds).

[0138] × ‥ Swelling peeling;

[0139] Regarding "swelling peeling," if the coating film swells and peels off rather than being dissolved during development, it was evaluated as × rather than break time.

[0140] In terms of development, it is desirable that the development time be within 30 seconds.

[0141] Outgas Amount Evaluation (Abbreviation in table: Outgas)

[0142] A photosensitive resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metal Co., Ltd.) to a thickness of 10 μm using an applicator, and after drying the film in a hot air dryer at 80°C for 30 minutes, ultraviolet light of 500 mJ / cm² was irradiated using an ultraviolet irradiator (GS YUASA: CS 30L-1). Afterwards, the copper foil was removed using an iron(III) chloride 45° Baume (manufactured by Jun Seikagaku Co., Ltd.) to obtain a cured product.

[0143] The amount of outgas when the cured material was heated in a furnace at 230°C for 30 minutes was measured using a P&T-GC (Purge and Trap Gas Chromatograph) and the following analysis method.

[0144] Measuring device:

[0145] P&T / JTD-505 III (Manufactured by Japan Analytical Industry)

[0146] GC / G1530A (Manufactured by Agilent Technologies)

[0147] Purge: 230℃ / 30min

[0148] Trap: -40℃

[0149] Column: HP-5MS 30m × 0.25mm id, df = 0.25㎛ (Manufactured by Agilent Technologies)

[0150] Carrier gas: He 1.2 mL / min (Constant flow mode)

[0151] Detector temperature: 300℃

[0152] Oven: 50℃ (2 min) - 300℃ (13 min), temperature increase 10℃ / min

[0153] Injection: Split (10:1)

[0154] Detector: FID (Manufactured by Agilent Technologies)

[0155] Sample amount: 4 mg

[0156] Next, the composition of the out-gas of the cured product was analyzed using thermal desorption GC-MS (gas chromatograph mass spectrometer) in the following manner.

[0157] Measuring device:

[0158] Thermal Desorption / JCI-22 (Manufactured by Japan Analytical Industry)

[0159] GC-MS / JMS-Q1500GC (Manufactured by JEOL)

[0160] Column: HP-5MS 30m × 0.25mm id, df = 0.25㎛ (Manufactured by Agilent Technologies)

[0161] Carrier gas: He 1.0 mL / min (Constant flow mode)

[0162] Thermal desorption temperature: 315℃

[0163] Heat removal time: 15 sec.

[0164] Oven: 50℃ (2 min) – 300℃ (3 min), temperature increase 10℃ / min

[0165] Injection: Split (30:1)

[0166] Ionization: EI

[0167] By thermal desorption GC-MS, it was found that polybasic anhydride (d) was generated as an outgas from the reactive polycarboxylic acid compound (A). For the peak attributed to polybasic anhydride (d), the peak area was calculated using P&T-GC and used as an indicator of the outgas amount (Area / mg).

[0168]

[0169]

[0170] An FID detector sensitive to carbon atoms is used for the quantitative determination of the out-gas amount. To compare the out-gas amounts of different polybasic anhydrides (d), the concept of relative sensitivity (effective number of carbons) in the FID detector was introduced. Specifically, the out-gas amount was calculated by dividing the obtained peak area by the effective number of carbons in the FID detector of the corresponding polybasic anhydride (d). The out-gas amount divided by the effective number of carbons of the polybasic anhydride is shown in Table 4. Furthermore, the effective number of carbons was calculated from the types and number of functional groups by creating Table 3 below based on the references listed below. (References [Supervised by Yoshio Umezawa, Tsuguo Sawada, and Hiroshi Nakamura; "Latest Separation, Purification, and Detection Methods," NTS (1997), p. 35])

[0171]

[0172] In addition, since the acid value of the reactive polycarboxylic acid compound (A) used in each example and comparative example is different, the amount of outgassing of the acid value was calculated and is shown in Table 4.

[0173]

[0174] From the above results, it can be said that the active energy beam curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has a lower amount of acid sugar outgassing and also excellent developability compared to the comparative resin composition.

Claims

Claim 1 A reactive polycarboxylic acid compound (A) obtained by reacting a reactive epoxycarboxylate compound (c), which is obtained by reacting a carboxylic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule with an epoxy resin (a) represented by the following formula (1) or (2), with a polybasic acid anhydride (d) represented by the following formula (3). (In the formula, n represents the mean value and a number from 0 to 10; G represents the glycidyl group) (In the formula, n represents an average value and a number from 0 to 10; P and R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and multiple P and R may be the same or different from each other; G represents a glycidyl group) (In Equation (3), R1 each independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; m represents an integer from 1 to 3) Claim 2 An active energy beam curable resin composition comprising the reactive polycarboxylic acid compound (A) described in claim 1. Claim 3 In paragraph 2, an active energy beam curable resin composition comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A). Claim 4 An active energy beam curable resin composition comprising a photopolymerization initiator in claim 2 or 3. Claim 5 In paragraph 2 or 3, an active energy beam curable resin composition which is a material for a display device. Claim 6 Cured product of the active energy beam curable resin composition described in paragraph 2 or 3.

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