Reactive polycarboxylic acid compounds, active energy ray curable resin compositions using the same, and cured products thereof.

Abstract

The purpose of the present invention is to provide: an active energy ray-curable resin composition which allows for patterning by photolithography and which has a low outgassing amount; and a cured product of the active energy ray-curable resin composition.　The present invention was arrived at upon finding that this problem is solved by a resin composition which uses a reaction product of a specific polybasic acid anhydride and an unsaturated group-containing carboxylic acid and a specific epoxy resin.

Description

Technical Field

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

Background Art

[0002] An organic EL display element utilizing electroluminescence of an organic compound is self-emissive, has no viewing angle dependency, has a fast response speed, and can be made thinner and lighter, and thus has many characteristics, and development for use in image display devices has been actively carried out.

[0003] For fabricating components of display devices such as organic EL displays, such as partition walls and planarization layers, a pattern formation technique by photolithography is used, and an active energy ray-curable resin composition is used.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, there has been a problem with outgassing from active energy ray-curable resin materials contaminating devices and manufacturing equipment, and there is a need for the development of active energy ray-curable resin materials with low outgassing. Therefore, the present invention aims to provide an active energy ray-curable resin composition and its cured product that can be patterned by photolithography and have low outgassing. More specifically, the present invention aims to provide an active energy ray-curable resin material with low outgassing per unit acid value. [Means for solving the problem]

[0006] In order to solve the aforementioned problems, the present inventors conducted diligent research and found that a resin and resin composition using a reaction product of a specific epoxy resin, an unsaturated group-containing carboxylic acid, and a specific polybasic acid anhydride solves the aforementioned problems, thus leading to the present invention.

[0007] In other words, the present invention is [1] A reactive polycarboxylic acid compound (A) obtained by reacting an epoxy resin (a) represented by the following formula (1) or (2) with a carboxylic acid compound (b) having both polymerizable ethylenically unsaturated groups and carboxyl groups in one molecule, and then reacting the reactive epoxy carboxylate compound (c) with a polybasic acid anhydride (d) represented by the following formula (3).

[0008] [ka] (In the formula, n represents the average value and is a number between 0 and 10. G represents a glycidyl group.)

[0009] [ka] (In the formula, n represents the average value and is a number between 0 and 10. P and R each independently represent one of the following: a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, or an aryl group. Multiple P and R groups may be the same or different from each other. G represents a glycidyl group.)

[0010] [ka] (In formula (3), R1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer from 1 to 3.) An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [2][1]. [3] The active energy ray curable resin composition according to [2], comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A). [4] An active energy ray curable resin composition according to [2] or [3], comprising a photopolymerization initiator. [5] An active energy ray curable resin composition according to any one of [2] to [4], which is a material for a display device. A cured product of an active energy ray curable resin composition as described in any one of items [6][2] to [5]. [Effects of the Invention]

[0011] The active energy ray curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention provides a cured resin product that exhibits excellent developability, allows for patterning by photolithography, and has low outgassing. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. The reactive polycarboxylic acid compound (A) of the present invention can be 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 both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule to obtain a reactive epoxy carboxylate compound (c). Then, it can be obtained by reacting it with a polybasic acid anhydride (d) represented by the following formula (3).

[0013] [ka]

[0014] In the above formula (1), n represents an average value and indicates a number from 0 to 10.

[0015] G represents a glycidyl group.

[0016] [Chemical formula]

[0017] In the above formula (2), n represents an average value and indicates a number from 0 to 10.

[0018] P and R each independently represent a hydrogen atom, a halogen atom, a C1-C8 alkyl group, or an aryl group, and multiple P and R groups may be the same or different from each other. The C1-C8 alkyl group may be linear, branched, or cyclic alkyl group, and specifically include 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-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 2-pentyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 3-pentyl group, and 3-ethylpentyl group. Examples include tan-3-yl group, cyclopentyl group, 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. Examples of the aryl group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,5-xylyl group, naphthyl group, and anthyl group. P and R are preferably hydrogen atoms.

[0019] G represents a glycidyl group.

[0020] [ka]

[0021] In formula (3) above, R1 independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic alkyl groups. Specifically, these include 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, and 5-dimethylbutyl group. Examples include clopentyl group, 3-ethylcyclopentyl group, hexyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, bicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octane-2-yl group, adamantane-2-yl group, bicyclo[2.2.1]heptan-2-yl group, adamantane-1-yl group, etc. R1 is preferably hydrogen. m represents an integer from 1 to 3.

[0022] First, we will explain the carboxylation step, which involves imparting reactivity to a carboxylate compound to obtain a reactive epoxy carboxylate compound (c).

[0023] The epoxy resin (a) used in the present invention is an epoxy resin represented by formula (1) or (2) above. The epoxy resin represented by formula (1) is generally available under various trade names, such as EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 from Nippon Kayaku Co., Ltd., Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-690, Epiclon N-695, Epiclon N-665-EXP, Epiclon N-672-EXP from DIC Corporation, and YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A from Nippon Steel Chemical & Material Co., Ltd.

[0024] The epoxy resin represented by formula (2) is generally available under various trade names, such as NC-3000, NC-3100, NC-3000-L, NC-3000-H, NC-3000-LC, and NC-3000-LLC, manufactured by Nippon Kayaku Co., Ltd.

[0025] In the present invention, a carboxylic acid compound (b) (hereinafter also simply referred to as "carboxylic acid compound (b)") having both a polymerizable ethylenically unsaturated group and a carboxyl group in a single molecule is reacted to impart reactivity to active energy rays. There are no restrictions as long as there is one or more ethylenically unsaturated groups and carboxyl groups in the molecule.

[0026] Examples of carboxylic acid compounds (b) that contain both polymerizable ethylenically unsaturated groups and carboxyl groups in a single molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or reaction products of saturated or unsaturated dibasic acids with unsaturated group-containing monoglycidyl compounds. Examples of (meth)acrylic acids mentioned above include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimers, semi-esters obtained by equimolar reaction of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having one hydroxyl group per molecule, semi-esters obtained by equimolar reaction of saturated or unsaturated dibasic acids with monoglycidyl (meth)acrylate derivatives, and other monocarboxylic acid compounds containing one carboxyl group per molecule. Furthermore, examples of (meth)acrylic acids include semi-esters obtained by equimolar reaction of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having multiple hydroxyl groups per molecule, and semi-esters obtained by equimolar reaction of saturated or unsaturated dibasic acids with glycidyl (meth)acrylate derivatives having multiple epoxy groups per molecule. Among these, (meth)acrylic acid is preferred.

[0027] Of these, considering the stability of the reaction between epoxy resin (a) and carboxylic acid compound (b), monocarboxylic acid is preferred as carboxylic acid compound (b), and even when monocarboxylic acid and polycarboxylic acid are used in combination, it is preferable that the value expressed as molar amount of monocarboxylic acid / molar amount of polycarboxylic acid is 15 or more. Most preferably, in terms of sensitivity when used as an active energy ray curable resin composition, are (meth)acrylic acid, the reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid.

[0028] The ratio of epoxy resin (a) to carboxylic acid compound (b) in this carboxylation reaction should be adjusted as appropriate depending on the application. Specifically, if all epoxy groups are carboxylated, no unreacted epoxy groups remain, resulting in high storage stability as a reactive epoxy carboxylate compound (c). In this case, only the reactivity due to the introduced double bond is utilized.

[0029] On the other hand, by reducing the amount of carboxylic acid compound (b) used and leaving unreacted residual epoxy groups, it is possible to utilize a combination of reactivity due to the introduced unsaturated bonds and reactions due to the residual epoxy groups, such as polymerization reactions catalyzed by photocations or thermal polymerization reactions. However, in this case, care should be taken when considering the storage and production conditions of the reactive epoxy carboxylate compound (c).

[0030] When producing a reactive epoxy carboxylate compound (c) that does not leave any epoxy groups, it is preferable that the total amount of carboxylic acid compound (b) is 90 to 120 equivalents per equivalent of epoxy resin (a). Within this range, production can be carried out under relatively stable conditions. If the amount of carboxylic acid compound charged is greater than this, it is undesirable because excess carboxylic acid compound (b) and reactive epoxy carboxylate compound (c) will remain.

[0031] Furthermore, if epoxy groups are to remain, the total amount of carboxylic acid compound (b) is preferably 20 to 90 equivalents per equivalent of epoxy resin (a). If this range is exceeded, the combined curing effect will be reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and the long-term stability of the reactive epoxy carboxylate compound (c).

[0032] The carboxylation reaction can be carried out without a solvent, or after dilution with a solvent. The solvent that can be used is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

[0033] The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resulting resin, but preferably it is used to achieve a solid content of 90-20% by mass, more preferably 80-30% by mass.

[0034] Specific 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.

[0035] Examples of ester 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 monoacetate, 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 polycarboxylate alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate.

[0036] 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, and triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

[0037] Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0038] In addition, the process can be carried out using a reactive compound (B) other than the reactive polycarboxylic acid compound (A) described later (hereinafter also simply referred to as "reactive compound (B)"), either alone or in a mixture of organic solvents. In this case, it is preferable because, when used as a curable resin composition, it can be used directly as a composition.

[0039] During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of catalyst used is 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the reactants, i.e., epoxy resin (a), carboxylic acid compound (b), and optionally solvents and other reactants. The reaction temperature is preferably 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, triphenylstybin, methyltriphenylstybin, chromium octanoate, zirconium octanoate, and other known basic catalysts.

[0040] Furthermore, a thermal polymerization inhibitor can also be used. Preferred thermal polymerization inhibitors include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-tert-butyl-4-hydroxytoluene.

[0041] The carboxylation reaction is terminated when the acid value of the sample reaches 5 mg KOH / g or less, preferably 3 mg KOH / g or less, while sampling is performed as needed.

[0042] The preferred molecular weight range for the reactive epoxy carboxylate compound (d) obtained in this way is a polystyrene-equivalent weight-average molecular weight in GPC 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 fully exhibited, and the coating properties are also good.

[0043] If the molecular weight is smaller than this, the toughness of the cured product will not be fully exhibited, and if it is too large, the viscosity will become high, making coating and other applications difficult.

[0044] Next, the acid addition step (hereinafter also simply referred to as "this acid addition reaction") will be described in detail. The acid addition step is carried out with the aim of introducing a carboxyl group into the reactive epoxy carboxylate compound (c) obtained in the previous step, as needed, to obtain a reactive polycarboxylic acid compound (A). That is, a carboxyl group is introduced via an ester bond by adding a polybasic acid anhydride (d) represented by formula (2) (hereinafter also simply referred to as "polybasic acid anhydride (d)") to the hydroxyl group produced by the carboxylation reaction.

[0045] Examples of C1-C10 alkyl groups in formula (2) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. In formula (2), R1 is preferably a hydrogen atom or a methyl group.

[0046] The polybasic acid anhydride (d) is preferably a compound represented by the following formula (3).

[0047] [ka]

[0048] The reaction to add 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 adjusted depending on the application.

[0049] The amount of polybasic acid anhydride (d) added is, for example, when using the reactive polycarboxylic acid compound (A) of the present invention as an alkaline aqueous solution developable resist material, preferably a calculated amount of polybasic acid anhydride (d) such that the solid content acid value (according to JIS K5601-2-1:1999) of the final reactive polycarboxylic acid compound (A) is 10 to 110 mg KOH / g, more preferably 20 to 100 mg KOH / g. When the solid content acid value is within this range, the alkaline aqueous solution developability of the active energy ray curable resin composition of the present invention is good. That is, it exhibits good patterning properties, a wide range of control over overdevelopment, and no excess acid anhydride remains.

[0050] During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of catalyst used is 0.1 to 10 parts by mass relative to the total amount of the reactants, namely the epoxy compound (a), the reactive epoxy carboxylate compound (c) obtained from the carboxylic acid compound (b), and the polybasic acid anhydride (d), and optionally the addition of a solvent and other substances. The reaction temperature is preferably 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstybin, methyltriphenylstybin, chromium octanoate, zirconium octanoate, and the like.

[0051] This acid addition reaction can be carried out without a solvent, or after dilution with a solvent. The solvent that can be used is not particularly limited as long as it is an inert solvent for the acid addition reaction. Furthermore, if the carboxylation reaction, which is the preceding step, uses a solvent, the product can be directly subjected to the subsequent acid addition reaction without removing the solvent, provided that the solvent is inert for both reactions. The solvent that can be used may be the same as that used in the carboxylation reaction.

[0052] The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resulting resin, but preferably it is used in an amount of 70 to 30% by mass, more preferably 60 to 40% by mass, relative to the solid content.

[0053] In addition, the process can be carried out using the reactive compound (B) alone or in a mixture of organic solvents. In this case, it is preferable because, when used as a curable resin composition, it can be used directly as a composition.

[0054] Furthermore, it is preferable to use the same thermal polymerization inhibitors as those exemplified in the carboxylation reaction described above.

[0055] This acid addition reaction is terminated when the acid value of the reactants falls within a range of plus or minus 10% of the set acid value, while sampling is performed as needed.

[0056] The preferred molecular weight range for the reactive polycarboxylic acid compound (A) obtained in this way is a polystyrene-based weight-average molecular weight in the range of 500 to 50,000 as measured by GPC (gel permeation chromatography), more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

[0057] If the molecular weight is smaller than this, the toughness of the cured product will not be fully exhibited, and if it is too large, the viscosity will become high, making coating and other applications difficult.

[0058] 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 are sensitive to both.

[0059] Examples of acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, and other epoxy acrylates, polyester acrylates, urethane acrylates, etc.

[0060] 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, and tetrahydrofurfuryl (meth)acrylate.

[0061] Polyfunctional (meth)acrylates include 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, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, and bisphenol di(meth)acrylate. Examples include di(meth)acrylate, an ε-caprolactone adduct of hydroxyvivariate neopene glycol, poly(meth)acrylate, a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and their ethylene oxide adducts, 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.

[0062] Suitable vinyl compounds 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, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimaallyl isocyanurate.

[0063] Furthermore, examples of so-called reactive oligomers include urethane acrylates that possess both a functional group sensitive to active energy rays and a urethane bond within the same molecule, polyester acrylates that similarly possess both a functional group sensitive to active energy rays and an ester bond within the same molecule, epoxy acrylates derived from epoxy resins that possess both a functional group sensitive to active energy rays within the same molecule, and reactive oligomers in which these bonds are used in combination.

[0064] Furthermore, there are generally no particular limitations on the cationic monomer as long as it is 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 (e.g., Union Carbide's "Cyracure UVR-6110"), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., Union Carbide's "ELR-4206"), limonene dioxide (e.g., Daicel Chemical Industries' "Celoxide 3000"), and Examples include lylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate (e.g., Union Carbide's "Cyracure UVR-6128"), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, and bis(3,4-epoxycyclohexyl) diethylsiloxane.

[0065] Of these, acrylates, which are radical-curable, are the most preferred reactive compound (B). In the case of cationic compounds, the carboxylic acid and epoxy group react, making it necessary to use a two-component mixture.

[0066] The reactive polycarboxylic acid compound (A) of the present invention and another reactive compound (B) can be mixed to obtain the active energy ray curable resin composition of the present invention. At this time, other components may be added as appropriate depending on the application.

[0067] The active energy ray curable resin composition of the present invention contains 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 another reactive compound (B). It may optionally contain 0 to 80 parts by mass of other components.

[0068] In addition, to adapt the active energy ray-curable resin composition of the present invention to various applications, other components may be added to the composition in an amount up to 70 parts by mass. Examples of other components include photopolymerization initiators, other additives, coloring materials, thermosetting catalysts, and volatile solvents added to adjust viscosity for purposes such as providing coating suitability.

[0069] The active energy ray curable resin composition of the present invention may further contain a photopolymerization initiator. A radical-type photopolymerization initiator and a cationic photopolymerization initiator are preferred as the photopolymerization initiator. Examples of radical-type photopolymerization initiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; and 2-ethylanthraquinone, 2-t-butylanthraquinone, and 2-chloroanthraquinone. Examples of commonly known radical-type photopolymerization initiators include anthraquinones such as quinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0070] 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 initiators, borate initiators, and other photoacid generators.

[0071] Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (e.g., San-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphonate (e.g., CyracureUVI-6990 manufactured by UnionCarbide Inc.) and triphenylsulfonium hexafluoroantimonate (e.g., CyracureUVI-6974 manufactured by UnionCarbide Inc.). Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate.

[0072] Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (e.g., TrigonalPI from AKZO), 2,2-dichloro-1-4-(phenoxyphenyl)ethanone (e.g., Sandray1000 from Sandoz), and α,α,α-tribromomethylphenylsulfone (e.g., BMPS from Seitetsu Kagaku Co., Ltd.). Examples of triazine-based initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (e.g., Triazine A from Panchim), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (e.g., Triazine PMS from Panchim), 2,4-trichloromethyl-(piperonyl)-6-triazine (e.g., Triazine PP from Panchim), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (e.g., Triazine B from Panchim), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (e.g., Sanwa Chemical Co., Ltd.), and 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (e.g., Sanwa Chemical Co., Ltd.).

[0073] Examples of borate-based photopolymerization initiators include NK-3876 and NK-3881 from Nippon Photosensitive Dye Co., Ltd., while other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (e.g., biimidazole from Kurogane Chemical Co., Ltd.), 2,2-azobis(2-amino-propane)dihydrochloride (e.g., V50 from Wako Pure Chemical Industries, Ltd.), and 2,2-azobis[2-(imidazolin-2yl)propane Examples include dihydrochlorides (such as VA044 from Wako Pure Chemical Industries, Ltd.), [eta-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,eta)-(methylethyl)-benzene]iron(II) hexafluorophosphonate (such as Irgacure261 from CibaGeigy), and bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridine-1-yl)phenyl]titanium (such as CGI-784 from CibaGeigy).

[0074] In addition, azo initiators such as azobisisobutyronitrile and heat-sensitive peroxide radical initiators such as benzoyl peroxide may be used in combination. Furthermore, both radical and cationic photopolymerization initiators may be used in combination. Photopolymerization initiators can be used individually or in combination of two or more types.

[0075] Of these, considering the properties of the reactive polycarboxylic acid compound (A) of the present invention, a radical-type photopolymerization initiator is particularly preferred.

[0076] Furthermore, the active energy ray curable resin composition of the present invention may contain coloring pigments. As coloring pigments, for example, non-coloring pigments, so-called extender pigments, may also be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, and carbon black.

[0077] Furthermore, the active energy ray curable resin composition of the present invention may contain other additives as needed. Other additives that can be used include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as aerosil, silicone-based and fluorine-based leveling agents and defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, and the like.

[0078] In addition, resins that do not react to active energy rays (so-called inert polymers) can also be used, such as 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 modified versions thereof. These are preferably used in amounts up to 40 parts by mass in the resin composition.

[0079] In particular, when using a reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use a commonly known epoxy resin as a resin that does not react to active energy rays. This is because, even after reaction and curing with active energy rays, carboxyl groups derived from the reactive polycarboxylic acid compound (A) remain, resulting in the cured product having poor water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated, forming an even stronger cross-linked structure. The commonly known epoxy resin can be the cationic reactive monomer mentioned above.

[0080] Furthermore, depending on the intended use, a volatile solvent may be added to the resin composition in an amount of up to 50 parts by mass, and more preferably up to 35 parts by mass, to adjust the viscosity.

[0081] The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and laser rays, and particle beams such as alpha rays, beta rays, and electron beams. Considering the preferred applications of the present invention, ultraviolet rays, laser rays, visible light, or electron beams are preferred among these.

[0082] In the present invention, the display device material is a material used in display elements such as liquid crystal displays, organic EL displays, and electronic paper. Specific applications include spacers, protective films, planarizing films, interlayer insulating films, and partitioning materials. Among these, the display device according to one embodiment of the present invention is preferably an organic EL display.

[0083] The present invention also includes a cured product obtained by irradiating the above-mentioned curable resin composition with active energy rays, and a multilayer material having a layer of the cured product.

[0084] Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water-developable resist material composition, taking advantage of its characteristic of being soluble in alkaline aqueous solutions.

[0085] In the present invention, a resist material composition refers to an active energy ray-sensitive composition that is formed by creating a film layer of the composition on a substrate, and then partially irradiating it with active energy rays such as ultraviolet light, and using the difference in physical properties between the irradiated and unirradiated areas to create a drawing. Specifically, it is a composition used for the purpose of removing the irradiated or unirradiated areas by some method, such as dissolving them with a solvent or alkaline solution, and then performing a drawing.

[0086] The active energy ray curable resin composition, which is a resist material composition of the present invention, can be applied to various patternable materials. For example, it is particularly useful as a solder resist material and an interlayer insulating material for build-up methods. Furthermore, it can be used as an optical waveguide in electrical, electronic, and optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates.

[0087] Particularly suitable applications include a wide range of applications requiring resin compositions, such as photosensitive films, photosensitive films with supports, insulating resin sheets like prepregs, circuit boards (laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component embedding resins, color resists, color filters, and black matrices, taking advantage of its excellent heat resistance and developability.

[0088] Furthermore, it can be suitably used in resin compositions for insulating layers of multilayer printed circuit boards (multilayer printed circuit boards using a cured photosensitive resin composition as the insulating layer), resin compositions for interlayer insulating layers (multilayer printed circuit boards using a cured photosensitive resin composition as the interlayer insulating layer), and resin compositions for plating (multilayer printed circuit boards with plating formed on a cured photosensitive resin composition).

[0089] Patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows: The curable resin composition of the present invention is applied to a substrate to a film thickness of 0.1 to 200 μm by methods such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, and spin coating. The coating film is then dried at a temperature of typically 50 to 110°C, preferably 60 to 100°C, to form a coating film. Subsequently, high-energy rays such as ultraviolet light are applied directly or indirectly to the coating film through a photomask with an exposure pattern formed on it, typically at a rate of 10 to 2000 mJ / cm². 2 By irradiating with a moderate intensity and using the developing solution described later, the desired pattern can be obtained by methods such as spraying, vibrating immersion, paddle, or brushing.

[0090] As the alkaline aqueous solution used for the above development, inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate can be used, as well as organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine. These aqueous solutions may further contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0091] In addition, it is particularly suitable for use in dry films where mechanical strength before the curing reaction by active energy rays is required. That is, because the balance of hydroxyl groups and epoxy groups in 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 despite having a relatively high molecular weight.

[0092] There are no particular restrictions on the method of forming the coating, but various coating methods such as gravure printing (intaglio printing), flexographic printing (relief printing), screen printing (stencil printing), offset printing (planographic printing), roll coaters, knife coaters, die coaters, curtain coaters, and spin coaters can be arbitrarily adopted.

[0093] The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays and curing it. [Examples]

[0094] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, % refers to mass %.

[0095] The softening point, epoxy equivalent, and acid value were measured under the following conditions. 1) Epoxy equivalent: Measured according to the method in accordance with JIS K7236:2001. 2) Softening point: Measured according to the method in accordance with JIS K7234:1986. 3) Acid value: Measured according to the method in accordance with JIS K0070:1992. 4) The GPC (gel permeation chromatography) measurement conditions are as follows: Model: TOSOH HLC-8220GPC Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C Detector: RI (Differential Refractometer) Molecular weight standard: Polystyrene

[0096] (Synthesis Example 1): Synthesis of reactive epoxy carboxylate compound (c) 218 g of cresol novolac 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 carboxylic acid compound (b) were added. 1.25 g of triphenylphosphine was added as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent to a solid content of 70% by mass. The mixture was reacted at 100°C for 24 hours to obtain a reactive epoxy carboxylate compound (c) solution.

[0097] (Example 1-1): Preparation of reactive polycarboxylic acid compound (A-1) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 2.56 g of trimellitic anhydride (d) and propylene glycol monomethyl ether monoacetate were added as a solvent to achieve a solid content of 50%. An acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-1) solution with a solid content acid value of 39.5 mg·KOH / g. The solid content acid value (mg·KOH / g) was measured in solution and converted to a value in solid content.

[0098] (Comparative Example 1-1): Preparation of reactive polycarboxylic acid compound (A-2) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 4.11 g of phthalic anhydride (d) and propylene glycol monomethyl ether monoacetate were added as a solvent to achieve a solid content of 50%. An acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-2) solution with a solid content acid value of 40.6 mg·KOH / g. The solid content acid value (mg·KOH / g) was measured in solution and converted to a value in solid content.

[0099] (Comparative Example 1-2): Preparation of reactive polycarboxylic acid compounds (A-3) To 50.0 g of the reactive epoxycarboxylate compound (c) solution 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 reactive polycarboxylic acid compound (A-3) solution with a solid content acid value of 42.2 mg·KOH / g. The solid content acid value (mg·KOH / g) was measured in solution and converted to a value in solid content.

[0100] (Synthesis Example 2): Synthesis of reactive epoxy carboxylate compound (c) 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 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 a solid content of 70% by mass. The mixture was reacted at 100°C for 24 hours to obtain a reactive epoxy carboxylate compound (c) solution.

[0101] (Examples 1-2): Preparation of reactive polycarboxylic acid compounds (A-4) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 2, 3.98 g of trimellitic anhydride (d) and propylene glycol monomethyl ether monoacetate were added as a solvent to achieve a solid content of 50%. An acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-4) solution with a solid content acid value of 61.0 mg·KOH / g. The solid content acid value (mg·KOH / g) was measured in solution and converted to a value in solid content.

[0102] (Comparative Example 1-2): Preparation of reactive polycarboxylic acid compounds (A-5) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 2, 6.76 g of THPA (1,2,3,6-tetrahydrophthalic anhydride) as the polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as the solvent to achieve a solid content of 50% were added, and an acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-5) solution with a solid content acid value of 60.5 mg·KOH / g. The solid content acid value (mg·KOH / g) was measured in solution and converted to a value in solid content.

[0103] (Example 3 and Comparative Example 3): Preparation of resin composition, evaluation of developability, and evaluation of outgassing amount. 2.00 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Examples 1-1 and 1-2, 0.67 g of DPHA (trade 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.

[0104] Each item of the evaluation criteria will be described in detail.

[0105] Developability evaluation (abbreviation in table: Developability) The resin composition was applied to a glass substrate using a spin coater and then dried in a hot air dryer at 80°C for 5 minutes. Subsequently, spray development was performed with a 1% sodium carbonate aqueous solution (spray pressure 0.2 MPa), and the developability was evaluated by the time it took for the coating film to completely dissolve, known as the break time (unit: seconds). × ··Swelling and peeling; Regarding "swelling and peeling," if the coating swelled and peeled off during development instead of dissolving, it was evaluated as a failure (×) rather than requiring a break time. In terms of developability, a development time of 30 seconds or less is preferable.

[0106] Outgassing volume evaluation (abbreviated as "outgass" in the table) The photosensitive resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 10 μm using an applicator. The coating was dried in a hot air dryer at 80°C for 30 minutes, and then exposed to ultraviolet light at 500 mJ / cm² using a UV irradiator (GS YUASA: CS 30L-1). 2 The copper foil was then irradiated with ultraviolet light. Subsequently, the copper foil was removed with iron(III) chloride 45° Baume (manufactured by Junsei Chemical Co., Ltd.) to obtain a cured product.

[0107] The amount of outgassing when the cured material was heated in a heating furnace at 230°C for 30 minutes was measured using P&T-GC (purge and trap gas chromatography) with the following analytical method. Measuring device: P&T / JTD-505III (manufactured by Japan Analytical Industry) GC / G1530A (manufactured by Agilent Technologies) Purge: 230℃ / 30min Trap: -40℃ Column: HP-5MS 30m x 0.25mm id,df=0.25μm (manufactured by Agilent Technologies) Carrier gas: He 1.2 mL / min (Constant flow mode) Detector temperature: 300℃ Oven: 50℃ (2 min) - 300℃ (13 min), heating rate 10℃ / min Injection: Split (10:1) Detector: FID (manufactured by Agilent Technologies) Sample quantity: 4 mg

[0108] Next, the components of the outgassed material from the hardened product were analyzed using thermal desorption GC-MS (gas chromatograph-mass spectrometer) in the following manner. Measuring device: Thermal desorption / JCI-22 (manufactured by Japan Analytical Industry) GC-MS / JMS-Q1500GC (manufactured by JEOL) Column: HP-5MS 30m x 0.25mm id,df=0.25μm (manufactured by Agilent Technologies) Carrier gas: He 1.0 mL / min (Constant flow mode) Thermal desorption temperature: 315℃ Thermal desorption time: 15sec. Oven: 50℃ (2 min) - 300℃ (3 min), heating rate 10℃ / min Injection: Split (30:1) Ionization: EI

[0109] Thermal desorption GC-MS revealed that polybasic acid anhydride (d) was generated as outgassing from the reactive polycarboxylic acid compound (A). The peak area of ​​the peak assigned to polybasic acid anhydride (d) was determined by P&T-GC and used as an indicator of the outgassing amount (Area / mg).

[0110] [Table 1]

[0111] [Table 2]

[0112] An FID detector sensitive to carbon atoms was used to quantify the amount of outgassing. To compare the outgassing amounts of different polybasic acid anhydrides (d), the concept of relative sensitivity (effective carbon number) in the FID detector was introduced. Specifically, the obtained peak area was divided by the effective carbon number of the corresponding polybasic acid anhydride (d) in the FID detector, and the outgassing amount was calculated. Table 4 shows the outgassing amounts divided by the effective carbon number of polybasic acid anhydrides. The effective carbon number was calculated from the type and number of functional groups, based on the following reference [Yoshio Umezawa, Tsuguo Sawada, Hiroshi Nakamura (eds.); "Latest Separation, Purification, and Detection Methods", NTS (1997), p.35]].

[0113] [Table 3]

[0114] Furthermore, since the acid values ​​of the reactive polycarboxylic acid compound (A) used in each example and comparative example differed, the amount of outgassing per unit acid value was calculated and is shown in Table 4.

[0115] [Table 4]

[0116] Based on the above results, it can be said that the active energy ray curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has a lower outgassing rate per unit acid value and superior developability compared to the comparative resin composition.

Claims

1. A reactive polycarboxylic acid compound (A) is obtained by reacting an epoxy resin (a) represented by the following formula (1) or (2) with a carboxylic acid compound (b) having both polymerizable ethylenically unsaturated groups and carboxyl groups in one molecule, to obtain a reactive epoxy carboxylate compound (c), which is then reacted with a polybasic acid anhydride (d) represented by the following formula (3), The carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule is (meth)acrylic acid. A reactive polycarboxylic acid compound (A) having a solid content acid value of 20 to 61.0 mg / g. 【Chemistry 1】 (In formula (1), n ​​represents the average value and is a number between 0 and 10. G represents a glycidyl group.) 【Chemistry 2】 (In formula (2), n represents the average value and is a number between 0 and 10. P and R each independently represent one of the following: a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. Multiple P and R values ​​may be the same or different from each other. G represents a glycidyl group.) 【Transformation 3】 (In formula (3), R １ Each of these independently represents a hydrogen atom and an alkyl group with 1 to 10 carbon atoms. m represents an integer from 1 to 3.

2. An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in claim 1.

3. The active energy ray curable resin composition according to claim 2, comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A).

4. The active energy ray curable resin composition according to claim 2 or 3, comprising a photopolymerization initiator.

5. The active energy ray curable resin composition according to claim 2 or 3, which is a material for a display device.

6. A cured product of the active energy ray curable resin composition according to claim 2 or 3.

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