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

Abstract

To provide an active energy ray-curable resin composition from which a cured film excellent in heat resistance and developability is given.SOLUTION: A resin composition contains an active energy ray-reactive polycarboxylic acid compound (A) obtained by reacting only a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, or an active energy ray-reactive epoxy carboxylate compound (d) obtained by reacting only a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule with only a compound (c) having both a hydroxyl group and a carboxy group in one molecule, with an epoxy resin (a), with a polybasic acid anhydride (e) represented by a following formula (2), and a coloring pigment. (In the formula (2), R1 each independently represents a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)SELECTED DRAWING: None

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 color resist, a resist material for a color filter, and a black matrix material, an active energy ray-curable resin composition containing the same, and a cured product thereof.

Background Art

[0002] Printed wiring boards aim at miniaturization and weight reduction of portable devices and improvement of communication speed, and are required to have high precision and high density. Along with this, the requirements for solder resists that coat the circuit itself are becoming increasingly sophisticated. Performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining higher heat resistance and thermal stability than conventional requirements is required, and a film-forming material having a tougher cured physical property is demanded.

[0003] As these materials, a carboxylate compound obtained by reacting a general epoxy resin with a compound having a carboxylic acid and a hydroxyl group and acrylic acid together is known as a material having excellent developability while having a low acid value, and it is also known that this compound has resist ink suitability (Patent Document 1).

[0004] On the other hand, acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton is generally known as a material showing high toughness after curing, and its use as a solder resist has also been studied (Patent Document 2).

[0005] In addition, attempts have been made to apply acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton to a black matrix resist used for liquid crystal display panels and the like by dispersing carbon black or the like therein (Patent Document 3). In addition, phenolic aralkyl type acid-modified epoxy acrylate compounds that are excellent in the dispersibility of coloring pigments and the like and have good development characteristics even at a high pigment concentration have also been studied (Patent Document 4).

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 06-324490 [Patent Document 2] Japanese Patent Application Laid-Open No. 09-211860 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-055814 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-163368 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] However, although the acid-modified epoxy acrylate having a phenolic aralkyl type epoxy resin as a basic skeleton allows coloring pigments such as carbon black to be well compatible with the resin and the pigments to be dispersed, further improvement in developability and higher heat resistance are required. Therefore, an object of the present invention is to improve the above-mentioned problems of the prior art and to provide a highly heat-resistant acid-modified epoxy acrylate compound that is excellent in the dispersibility of coloring pigments and the like and has good development characteristics even at a high pigment concentration, and an active energy ray-curable resin composition containing the same. [Means for Solving the Problems]

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition using a reaction product of an epoxy resin having a polycyclic hydrocarbon group, an unsaturated group-containing carboxylic acid, and a compound having both a hydroxyl group and a carboxyl group in one molecule as necessary, and a reaction product with a specific polybasic acid anhydride solves the above problems, and thus the present invention has been achieved.

[0009] That is, the present invention is [1] A reactive polycarboxylic acid compound (A) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule and, if necessary, a compound (c) having both a hydroxy group and a carboxy group in one molecule, is reacted with a polybasic acid anhydride (e) represented by the following formula (2) or formula (3).

[0010] [Chemical formula]

[0011] (In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) / (II) is 1 to 3. G represents a glycidyl group. n is the average value of the repeating number and is a positive number where 0 < n ≤ 5.)

[0012] [Chemical formula]

[0013] (In formula (2), each R1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer from 1 to 3.) [2] An active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) described in the previous item [1]. [3] The active energy ray-curable resin composition described in the previous item [2], which contains a reactive compound (B) other than the reactive polycarboxylic acid compound (A). [4] The active energy ray-curable resin composition described in the previous item [2] or [3], which contains a photopolymerization initiator. [5] The active energy ray-curable resin composition described in any one of the previous items [2] to [4], which is a molding material. [6] The active energy ray-curable resin composition described in any one of the previous items [2] to [4], which is a film-forming material. [7] The active energy ray-curable resin composition described in any one of the previous items [2] to [4], which is a resist material composition. [8] The cured product of the active energy ray-curable resin composition according to any one of the preceding items [2] to [7], [9] An article overcoated with the cured product according to the preceding item [8], relates to the following.

Effects of the Invention

[0014] The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only gives a tough cured product but also has excellent resin physical properties even in a state where only the solvent is dried. Further, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays is excellent in heat resistance and can be finely developed with alkali, so it is suitable as a molding material, a film-forming material, and a resist material. Also, due to the high affinity with coloring pigments, the reactive polycarboxylic acid compound of the present invention and the active energy ray-curable resin composition containing the same exhibit good developability even at a high pigment concentration, so they are suitable for color resists, resist materials for color filters, particularly black matrix materials, etc.

[0015] Furthermore, the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has thermal and mechanical toughness, good storage stability, and high reliability to withstand high temperature and high humidity and thermal shock, so it is particularly used in applications such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides that require high reliability.

Modes for Carrying Out the Invention

[0016] Hereinafter, the present invention will be described in detail. 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) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (c) having both a hydroxy group and a carboxy group in one molecule to obtain a reactive epoxy carboxylate compound (d). Subsequently, it can be obtained by reacting a polybasic acid anhydride (e) represented by the following formula (2) or formula (3).

[0017] [Chemical formula]

[0018] (In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) / (II) is 1 to 3. G represents a glycidyl group. n is the average value of the repeating number and is a positive number where 0 < n ≤ 5.)

[0019] [Chemical formula]

[0020] (In formula (2), each R1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)

[0021] First, the carboxylation step for imparting reactivity to the carboxylate compound to obtain the reactive epoxy carboxylate compound (d) will be described.

[0022] The epoxy resin (a) represented by the above formula (1) used in the present invention (hereinafter, also simply referred to as "epoxy resin (a)") is generally available under various trade names, for example, NC-3500 (manufactured by Nippon Kayaku Co., Ltd.), etc. Of the Ar in the above formula (1), (I) may be any of the ortho, meta, and para isomers. In the present invention, the meta isomer represented by the following formula (4) is preferred.

[0023] [Chemical formula]

[0024] In the present invention, a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule (hereinafter, also simply referred to as "carboxylic acid compound (b)") is caused to react in order to impart reactivity to active energy rays. There is no limitation as long as there is at least one ethylenically unsaturated group and at least one carboxy group in the molecule.

[0025] Examples of the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of (meth)acrylic acids include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, half-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid anhydride and a (meth)acrylate derivative having one hydroxyl group in one molecule, monocarboxylic acid compounds containing one carboxy group in one molecule such as half-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid and monoglycidyl (meth)acrylate derivatives, half-esters which are equimolar reaction products of a (meth)acrylate derivative having a plurality of hydroxyl groups in one molecule, and polycarboxylic acid compounds having a plurality of carboxy groups in one molecule such as half-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid and glycidyl (meth)acrylate derivatives having a plurality of epoxy groups.

[0026] Among these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarboxylic acid. Even when a monocarboxylic acid and a polycarboxylic acid are used in combination, the value represented by the molar amount of the monocarboxylic acid / molar amount of the polycarboxylic acid is preferably 15 or more. Most preferably, from the viewpoint of sensitivity when used as an active energy ray-curable resin composition, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid can be mentioned. As the compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule, those having no hydroxyl group in the compound are preferred.

[0027] The compound (c) having a hydroxyl group and a carboxy group in one molecule used in the present invention (hereinafter also simply referred to as "compound (c)") is made to react for the purpose of introducing a hydroxyl group into a carboxylate compound. These include a compound having one hydroxyl group and one carboxy group in one molecule, a compound having two or more hydroxyl groups and one carboxy group in one molecule, and a compound having one or more hydroxyl groups and two or more carboxy groups in one molecule. Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like. Examples of the compound having two or more hydroxyl groups and one carboxy group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Examples of the compound having one or more hydroxyl groups and two or more carboxy groups in one molecule include hydroxyphthalic acid and the like. Among these, those having two or more hydroxyl groups in one molecule are preferred in consideration of the effects of the present invention. Furthermore, from the viewpoint of the stability of the carboxylation reaction, it is preferred that there is one carboxy group in one molecule. Most preferably, those having two hydroxyl groups and one carboxy group in one molecule are preferred. In consideration of the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As the compound having one or more hydroxyl groups and one or more carboxy groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferred.

[0028] The charging ratios of the epoxy resin (a), the carboxylic acid compound (b), and the compound (c) in this carboxylation reaction should be appropriately changed according to the application. That is, when all epoxy groups are carboxylated, since no unreacted epoxy groups remain, the storage stability as the reactive epoxy carboxylate compound (d) is high. In this case, only the reactivity due to the introduced double bond will be utilized.

[0029] On the other hand, by reducing the charging amounts of the carboxylic acid compound (b) and the compound (c) to leave unreacted residual epoxy groups, it is also possible to comprehensively utilize the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy groups, such as the polymerization reaction by a photo cationic catalyst or a thermal polymerization reaction. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate compound (d) and the consideration of the manufacturing conditions.

[0030] When producing a reactive epoxy carboxylate compound (d) without leaving epoxy groups, it is preferable that the total of the carboxylic acid compound (b) and the compound (c) is 90 to 120 equivalent % with respect to 1 equivalent of the epoxy resin (a). If it is within this range, production under relatively stable conditions is possible. When the charging amount of the carboxylic acid compound is larger than this, it is not preferable because excessive carboxylic acid compounds (b) and (c) will remain.

[0031] Also, when leaving epoxy groups, it is preferable that the total of the carboxylic acid compound (b) and the compound (c) is 20 to 90 equivalent % with respect to 1 equivalent of the epoxy resin (a). If it deviates from this range, the effect of composite curing will be weakened. Of course, in this case, sufficient attention is required regarding gelation during the reaction and the stability over time of the reactive epoxy carboxylate compound (d).

[0032] The carboxylation reaction can be carried out without a solvent or by diluting with a solvent and then reacting. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

[0033] The amount of the solvent used is preferably adjusted appropriately according to the viscosity and use of the resulting resin, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% 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 petroleum ether, white gasoline, solvent naphtha, etc., which are mixtures thereof, ester solvents, ether solvents, ketone solvents, and the like.

[0035] Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, and 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 adipate.

[0036] Examples of ether 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 the ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, isophorone, and the like.

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

[0039] During the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b) and the compound (c), and optionally the solvent and other added substances. The reaction temperature at that time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate, and the like.

[0040] Also, a thermal polymerization inhibitor can be used. As the thermal polymerization inhibitor, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, and the like.

[0041] The carboxylation reaction is terminated at the point when the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling appropriately.

[0042] The preferable molecular weight range of the reactive epoxy carboxylate compound (d) thus obtained is such that the polystyrene-equivalent weight average molecular weight in GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

[0043] When the molecular weight is smaller than this, the toughness of the cured product cannot be fully exhibited, and when it is too large, the viscosity becomes high and coating and the like become 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 for the purpose of introducing a carboxy group into the reactive epoxy carboxylate compound (d) obtained in the previous step as needed to obtain a reactive polycarboxylic acid compound (A). That is, a polybasic acid anhydride (e) represented by the above formula (2) or (3) (hereinafter, also simply referred to as "polybasic acid anhydride (e)") is added to the hydroxyl group generated by the carboxylation reaction, and a carboxy group is introduced via an ester bond.

[0045] Examples of the alkyl group having 1 to 10 carbon atoms in the formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. As the hydrogen atom and R1 in the formula (2), a methyl group is preferable.

[0046] As the polybasic acid anhydride (e), a compound represented by the following formula (5) is preferable.

Chemical formula

[0047] The reaction for adding the polybasic acid anhydride (e) can be carried out by adding the polybasic acid anhydride (e) to the carboxylation reaction solution. The addition amount should be appropriately changed according to the use.

[0048] When the addition amount of the polybasic acid anhydride (e) is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali aqueous solution-developable resist material, it is preferable to charge a calculated value such that the solid content acid value (conforming to JIS K5601-2-1:1999) of the finally obtained reactive polycarboxylic acid compound (A) is preferably 20 to 120 mgKOH / g, more preferably 30 to 110 mgKOH / g. When the solid content acid value at this time is within this range, the alkali aqueous solution developability of the active energy ray curable resin composition of the present invention exhibits good developability. That is, it shows good patterning properties and a wide control range against overdevelopment, and no excessive acid anhydride remains.

[0049] During the reaction, it is preferable to use a catalyst to accelerate the reaction. The usage amount of the catalyst is 0.1 to 10 parts by mass based on the total amount of the reactants, that is, the reactive epoxy carboxylate compound (d) obtained from the epoxy compound (a), the carboxylic acid compound (b), and the compound (c), and the polybasic acid anhydride (e), and optionally a solvent and other substances added. The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate, and the like.

[0050] This acid addition reaction can be carried out without a solvent or by diluting with a solvent and then reacting. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. Also, when produced using a solvent in the previous carboxylation reaction, it can be directly subjected to the next acid addition reaction without removing the solvent, provided that it is inert to both reactions. The solvent that can be used may be the same as that which can be used in the carboxylation reaction.

[0051] The amount of the solvent used preferably should be appropriately adjusted according to the viscosity of the resulting resin and its use, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

[0052] In addition, it can be carried out in a single or mixed organic solvent such as the reactive compound (B). In this case, when used as a curable resin composition, it is preferable because it can be directly used as a composition.

[0053] Also, it is preferable to use a thermal polymerization inhibitor or the like similar to those exemplified in the carboxylation reaction.

[0054] This acid addition reaction is terminated at the point where the acid value of the reaction product is in the range of plus or minus 10% of the set acid value while appropriately sampling.

[0055] The preferable molecular weight range of the reactive polycarboxylic acid compound (A) thus obtained is such that the polystyrene-reduced weight average molecular weight in GPC (gel permeation chromatography) measurement is in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

[0056] When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is too large, the viscosity becomes high and coating and the like become difficult.

[0057] Specific examples of the reactive compound (B) that can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cation reaction type other epoxy compounds, and vinyl compounds sensitive to both.

[0058] Examples of the acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

[0059] 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, and the like.

[0060] Examples of 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, 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 ε-caprolactone adduct of hydroxybivalic acid neopentyl glycol, poly(meth)acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolamine 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, and the like.

[0061] 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, and the like. Examples of styrenes include styrene, methyl styrene, ethyl styrene, and the like. Examples of other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, and the like.

[0062] Furthermore, examples of so-called reactive oligomers include urethane acrylate having a functional group sensitive to active energy rays and a urethane bond in the same molecule, polyester acrylate having a functional group sensitive to active energy rays and an ester bond in the same molecule, epoxy acrylate derived from other epoxy resins and having a functional group sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination, and the like.

[0063] In addition, the cationic reactive monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (such as "Silacure UVR-6110" manufactured by Union Carbide Corporation), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide Corporation), limonene dioxide (such as "Celloxide 3000" manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxide, bis(3,4-epoxycyclohexyl)adipate (such as "Silacure UVR-6128" manufactured by Union Carbide Corporation), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane and the like can be mentioned.

[0064] Among these, as the reactive compound (B), acrylates which are radical curable types are most preferable. In the case of the cationic type, since the carboxylic acid reacts with the epoxy group, it is necessary to make it a two-component mixed type.

[0065] The reactive polycarboxylic acid compound (A) of the present invention and other 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 appropriately added according to the use.

[0066] 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, more preferably 3 to 90 parts by mass, of other reactive compounds (B) in the composition. Optionally, it may contain 0 to 80 parts by mass of other components as needed.

[0067] In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various applications, other components can be added to the composition up to 70 parts by weight. Examples of other components include photopolymerization initiators, other additives, coloring materials, curing accelerators, and volatile solvents added for viscosity adjustment for the purpose of imparting coating applicability, etc. Other components that can be used are exemplified below.

[0068] The active energy ray-curable resin composition of the present invention can further contain a photopolymerization initiator. As the photopolymerization initiator, a radical-type photopolymerization initiator or a cationic photopolymerization initiator is preferable. Examples of radical photoinitiators 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 - hydroxycyclohexyl phenyl ketone, and 2 - methyl - 1 - [4 - (methylthio)phenyl] - 2 - morpholino - propan - 1 - one; anthraquinones such as 2 - ethylanthraquinone, 2 - t - butylanthraquinone, 2 - chloroanthraquinone, 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’ - bis(methylamino)benzophenone; phosphine oxides such as 2,4,6 - trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6 - trimethylbenzoyl) - phenylphosphine oxide; and other known common radical photoinitiators.

[0069] Examples of cationic photoinitiators 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.

[0070] Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphate, N,N-diethylaminophenyldiazonium hexafluorophosphate (such as Sun-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.), etc. Examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, etc. Examples of sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphate (such as Cyracure UVI-6990 manufactured by Union Carbide), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide), etc. Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate, etc.

[0071] Examples of other halides include 2,2,2-trichloro-[1-4'-(dimethyl ethyl)phenyl]ethanone (such as Trigonal PI manufactured by AKZO), 2,2-dichloro-1-4-(phenoxyphenyl)ethanone (such as Sandray 1000 manufactured by Sandoz), α,α,α-tribromomethyl phenyl sulfone (such as BMPS manufactured by Seitetsu Kagaku Co., Ltd.), etc. Examples of triazine-based initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (such as Triazine A manufactured by Panchim), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl-(piperonyl)-6-triazine (such as Triazine PP manufactured by Panchim), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (such as Triazine B manufactured by Panchim), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd., etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.), etc.

[0072] Examples of borate-based photoinitiators include Nippon Kayaku's NK-3876 and NK-3881. Other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-bisimidazole (such as bisimidazole manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis(2-aminopropane) dihydrochloride (such as V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (such as VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [η5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,η)-(methylethyl)-benzene]iron(II) hexafluorophosphate (such as Irgacure261 manufactured by Ciba Geigy), bis(η5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyr-1-yl)phenyl]titanium (such as CGI-784 manufactured by Ciba Geigy), and the like.

[0073] In addition, azo-based initiators such as azobisisobutyronitrile and peroxide-based radical initiators sensitive to heat such as benzoyl peroxide may be used in combination. Also, both radical-based and cationic-based photoinitiators may be used in combination. The photoinitiator can be used alone or in combination of two or more.

[0074] Among these, considering the characteristics of the reactive polycarboxylic acid compound (A) of the present invention, radical-type photoinitiators are particularly preferred.

[0075] Furthermore, the active energy ray-curable resin composition of the present invention can contain a coloring pigment. As the coloring pigment, for example, those not intended for coloring, so-called extender pigments, can also be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, and the like.

[0076] Furthermore, the active energy ray-curable resin composition of the present invention can contain other additives as needed. Examples of other additives include heat-curing 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.

[0077] In addition to these, as resins that do not show reactivity to active energy rays (so-called inert polymers), for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40 parts by mass in the resin composition.

[0078] In particular, when attempting to use the reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use a known general epoxy resin as the resin that does not show reactivity to active energy rays. This is because after reaction and curing by active energy rays, carboxy groups derived from the reactive polycarboxylic acid compound (A) remain, and as a result, the cured product is inferior in water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxy groups are further carboxylated to form a stronger crosslinked structure. The known general epoxy resin can use the cationic reaction type monomer.

[0079] Also, depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent can be added to the resin composition in the range of up to 50 parts by mass, more preferably up to 35 parts by mass.

[0080] The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible light rays, infrared rays, X-rays, gamma rays, and laser light rays, and particle rays such as alpha rays, beta rays, and electron beams. Considering the preferred applications of the present invention, among these, ultraviolet rays, laser light rays, visible light rays, or electron beams are preferred.

[0081] In the present invention, the molding material refers to a material that is used for the purpose of putting an uncured composition into a mold or pressing the mold against it, forming an object, and then causing a curing reaction by active energy rays to form the mold, or irradiating the uncured composition with focused light such as a laser, causing a curing reaction, and forming the mold.

[0082] Specific applications include a sheet formed in a planar shape, a sealing material for protecting an element, a so-called nanoimprint material that performs fine molding by pressing a finely processed "mold" against an uncured composition, and further, peripheral sealing materials for light-emitting diodes and photoelectric conversion elements that have particularly strict thermal requirements, etc. are mentioned as suitable applications.

[0083] In the present invention, the film-forming material is used for the purpose of coating the surface of a substrate. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink, and offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, adhesive materials such as laminating adhesives and various adhesives for optical disks, and resist materials such as solder resist, etching resist, and resist for micromachines. Furthermore, a so-called dry film, which is obtained by temporarily coating a film-forming material on a peelable substrate, forming a film, and then laminating it on the original target substrate to form a film, also falls under the film-forming material.

[0084] 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.

[0085] Among these, since the introduction of the carboxy group of the reactive polycarboxylic acid compound (A) enhances the adhesion to the substrate, it is preferably used for coating a plastic substrate or a metal substrate.

[0086] Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkali-developable resist material composition, taking advantage of the characteristic that it becomes soluble in an aqueous alkali solution.

[0087] In the present invention, the resist material composition refers to an active energy ray-sensitive composition in which a film layer of the composition is formed on a substrate, and then, an active energy ray such as ultraviolet rays is partially irradiated, and drawing is attempted by utilizing the physical property difference between the irradiated portion and the non-irradiated portion. Specifically, it is a composition used for the purpose of removing the irradiated portion or the non-irradiated portion by dissolving it by some method, for example, with a solvent or an alkali solution, etc., and performing drawing.

[0088] The active energy ray-curable resin composition, which is the resist material composition of the present invention, can be applied to various materials capable of patterning, and is particularly useful for, for example, solder resist materials and interlayer insulating materials for build-up processes. Furthermore, it is also used for electric, electronic, and optical substrates such as printed wiring boards, optoelectronic substrates, and optical substrates as optical waveguides.

[0089] Particularly suitable applications include taking advantage of the characteristics of good heat resistance and developability, and using it in a wide range of applications where a resin composition is required, such as photosensitive films, photosensitive films with a support, insulating resin sheets such as prepregs, circuit boards (for laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, etc. Among them, since it can exhibit good developability even at a high pigment concentration, it can also be suitably used for color resists, resist materials for color filters, particularly black matrix materials, etc.

[0090] Furthermore, it can also be suitably used for resin compositions for insulating layers of multilayer printed wiring boards (multilayer printed wiring boards having cured products of photosensitive resin compositions as insulating layers), resin compositions for interlayer insulating layers (multilayer printed wiring boards having cured products of photosensitive resin compositions as interlayer insulating layers), resin compositions for plating formation (multilayer printed wiring boards having plating formed on cured products of photosensitive resin compositions), and the like.

[0091] Patterning using the active energy ray-curable resin composition of the present invention can be carried out, for example, as follows. The curable resin composition of the present invention is applied on a substrate at a film thickness of 0.1 to 200 μm by a method such as screen printing method, spray method, roll coating method, electrostatic coating method, curtain coating method, spin coating method, etc., and the coating film is usually dried at a temperature of 50 to 110 °C, preferably 60 to 100 °C, whereby a coating film can be formed. Then, high energy rays such as ultraviolet rays are irradiated directly or indirectly on the coating film through a photomask having an exposure pattern usually at a strength of 10 to 2000 mJ / cm 2 2, and a desired pattern can be obtained using a developer described later, for example, by spraying, vibrating immersion, paddle, brushing, etc.

[0092] 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 hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, etc., and organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, etc. can be used. Organic solvents, buffers, complexing agents, dyes or pigments can be further added to this aqueous solution.

[0093] In addition, it is particularly preferably used for dry film applications that require mechanical strength before the curing reaction by active energy rays. That is, since the balance between the hydroxyl groups and epoxy groups of the epoxy resin (a) used in the present invention is in a specific range, the reactive polycarboxylic acid compound (A) of the present invention can exhibit good developability despite having a relatively high molecular weight.

[0094] The method for forming the film is not particularly limited, and various coating methods such as gravure printing methods such as gravure, relief printing methods such as flexo, stencil printing methods such as silk screen, planographic printing methods such as offset, roll coater, knife coater, die coater, curtain coater, spin coater, etc. can be arbitrarily adopted.

[0095] 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 for curing.

[0096] An article overcoated with the active energy ray-curable resin composition of the present invention refers to a material having at least two or more layers obtained by forming and curing a film of the active energy ray-curable resin composition shown in the present invention on a substrate.

Examples

[0097] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples. In the examples, unless otherwise specified, % indicates mass%.

[0098] The softening point, epoxy equivalent, and acid value were measured under the following conditions. 1) Epoxy equivalent: Measured by a method according to JIS K7236:2001. 2) Softening point: Measured by a method according to JIS K7234:1986. 3) Acid value: Measured by a method according to JIS K0070:1992. 4) The measurement conditions for GPC 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

[0099] (Synthesis Examples 1 - 3): Synthesis of reactive epoxy carboxylate compound (d) 205 g of NC-3500 (manufactured by Nippon Kayaku Co., Ltd., softening point 70 °C, epoxy equivalent 205 g / eq.) was taken, and acrylic acid (AA) or methacrylic acid (MAA) in the amounts described in Table 1 as carboxylic acid compound (b) and dimethylolpropionic acid (hereinafter abbreviated as "DMPA") in the amount described in Table 1 as compound (c) were added. 3 g of triphenylphosphine was added as a catalyst, and propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content ratio was 80 mass%. The mixture was reacted at 100 °C for 24 hours to obtain a solution of reactive epoxy carboxylate compound (d).

[0100] [Table 1]

[0101] (Example 1, Comparative Example 1): Preparation of reactive polycarboxylic acid compound (A) To 200 g of the obtained solution of reactive epoxy carboxylate compound (d), the compounds described in Table 2 as polybasic acid anhydride (e), the amount (g), and propylene glycol monomethyl ether monoacetate were added as a solvent so that the solid content ratio was 65%. After heating to 100 °C, an acid addition reaction was carried out to obtain a solution of reactive polycarboxylic acid compound (A). The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid compound (A) was described in Table 2. The measurement of the solid content acid value (mgKOH / g) was carried out as a solution and converted to the value in terms of the solid content.

[0102] [Table 2]

[0103] HTMA: 1,2,4-Cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Company, Inc. NTA: Norbornanetricarboxylic anhydride, synthetic product, refer to Japanese Patent Publication No. 5532123 THPA: 1,2,3,6-Tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd. SA: Licacid SA Succinic anhydride, manufactured by Shin Nippon Rika Co., Ltd.

[0104] (Example 2 and Comparative Example 2): Preparation of resist material composition 54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 3.54 g of HX-220 (trade name: diacrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as the other reactive compound (B), 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as the photopolymerization initiator, 0.47 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 14.83 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as the curing agent component, 1.05 g of melamine as the thermosetting catalyst, and 20.95 g of methyl ethyl ketone as the concentration adjustment solvent were added, kneaded with a bead mill, and uniformly dispersed to obtain a resist material resin composition. The obtained composition was uniformly coated on a copper foil film serving as a support film by a roll coating method, passed through a hot air drying oven at a temperature of 70 °C, and a resin layer with a thickness of 30 μm was formed. Then, spray development was performed with a 1% aqueous sodium carbonate solution, and the development property was evaluated by the time until complete development, so-called break time (unit: second).

[0105]

Table 3

[0106] From the above results, the resist material composition using the reactive polycarboxylic acid compound (A) of the present invention has good developability compared to the compositions using the comparative reactive polycarboxylic acid compounds.

[0107] (Example 3 and Comparative Example 3): Evaluation of Heat Resistance 8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 0.24 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 0.01 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.403 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, 0.017 g of triphenylphosphine as a thermosetting catalyst, and 0.446 g of propylene glycol monomethyl ether monoacetate were added, uniformly applied to a polyimide film, passed through a hot air drying oven at a temperature of 80°C to form a resin layer with a thickness of 20 μm, and then exposed with an ultraviolet exposure apparatus (manufactured by Okou Seisakusho Co., Ltd., model HMW-680GW) to obtain a cured product. The produced cured product was cut out with a width of 5 mm. Then, it was set in a viscoelasticity measuring apparatus RSA-G2 manufactured by TA instruments, and in an air atmosphere, at a frequency of 10 Hz and a heating rate of 2°C / min., tanδ was measured, and the temperature at the maximum value of tanδ was taken as Tg.

[0108] [Table 4]

[0109] From the above results, it can be seen that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention is excellent in heat resistance compared to the comparative resin composition.

[0110] (Example 4 and Comparative Example 4): Evaluation of Pigment Dispersibility 20 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 5.0 g of DPHA (trade name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as the other reactive compound (B), 10 g of propylene glycol monomethyl ether acetate as the organic solvent, and 15 g or 10 g of Mitsubishi Carbon Black MA-100 as the coloring pigment were added and stirred. Further, 35 g of glass beads were added and dispersed for 1 hour with a paint shaker. The dispersion liquid after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater #2 and dried with a hot air dryer at 80°C for 10 minutes. The gloss of the coating film surface after drying was measured using a 60° reflection gloss meter (HORIBA IG-331 gloss meter), and the dispersibility of the carbon black was evaluated. The results are shown in Table 5. The higher the gloss value, the better the pigment dispersibility.

[0111]

Table 5

[0112] From the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 showed no change in the gloss value even when the content of the coloring pigment was high. It can be confirmed that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of the present invention is excellent without depending on the content of the coloring pigment, although the developability and heat resistance are improved.

[0113] From the above, the cured product of the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention is excellent in heat resistance and can be developed finely with alkali, so it is suitable as a molding material, a film-forming material, and a resist material. In particular, since it exhibits good developability even at a high pigment concentration, it is suitable for color resists, resist materials for color filters, especially black matrix materials, etc.

Claims

【Claim 1】 An active energy ray-reactive epoxy carboxylate compound (d) obtained by reacting only a carboxylic acid compound (b) having an ethylenically unsaturated group and a carboxy group polymerizable in one molecule or only a carboxylic acid compound (b) having an ethylenically unsaturated group and a carboxy group polymerizable in one molecule and a compound (c) having a hydroxy group and a carboxy group in one molecule with an epoxy resin (a) represented by the following formula (1), and reacting with a polybasic acid anhydride (e) represented by the following formula (2). A resin composition comprising an active energy ray-reactive polycarboxylic acid compound (A) and a coloring pigment, The resin composition wherein the content of the coloring pigment is 0.75 parts by mass or less based on the active energy ray-reactive polycarboxylic acid compound (A). 【Chemical 1】 (In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) to (II ) is (I) / (II) = 1 to 3. G represents a glycidyl group. n is the average value of the repeating number and is a positive number of 0 < n ≦ 5.) [Chemical Formula 2] (In formula (2), R １ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)

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