Reactive polycarboxylic acid compound, active energy ray-curable resin composition using same, cured product thereof, article, and printed wiring board

Abstract

The purpose of the present invention is to provide: a reactive polycarboxylic acid resin having good development characteristics while having both heat resistance and substrate adhesion; and an active energy ray-curable resin composition containing same.　As a result of intensive studies, the present inventors have found that a reactive polycarboxylic acid compound (A) obtained by reacting a reactive epoxy carboxylate compound (c) with a polybasic acid anhydride (d), the reactive epoxy carboxylate compound (c) being obtained by reacting an epoxy resin (a) represented by formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, solves the abovementioned problem, and have arrived at the present invention. (In the formula, n is an average value and represents a number of 1-15.)

Description

Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, cured product thereof, article, and printed wiring board

[0001] The present invention relates to a reactive polycarboxylic acid compound, an active energy ray-curable resin composition using the same, a cured product thereof, and uses thereof.

[0002] In recent years, with the high performance (miniaturization, weight reduction, and multifunctionalization) of electronic devices, the high integration of semiconductor components has been progressing. Along with this, the high density and high definition of semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, etc. have been advancing, and various studies have been conducted on component-embedded substrates in which components such as chip-chip capacitors are embedded in the substrate. As a surface protection film or interlayer insulating film used for semiconductor components, it is required that a via opening pattern for interlayer connection can be formed by development with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution, and that it can withstand substrate adhesion and high insulation while maintaining heat resistance and thermal stability. Therefore, a film-forming material having stronger toughness in cured properties is required.

[0003] As these materials, an unsaturated group-containing polycarboxylic acid resin, which is a reaction product of a general epoxy resin, a carboxylic acid compound having an acrylic acid and a hydroxyl group, and a polybasic acid anhydride, is known as a material having excellent developability while having a low acid value. Further, it is known that this resin has resist ink suitability (Patent Document 1).

[0004] On the other hand, in order to improve the adhesion to the substrate, studies have been conducted on adding a resin having a low glass transition temperature (Tg) to the composition (Patent Document 2). Although these photosensitive resin compositions have excellent developability and substrate adhesion, they do not satisfy the increasingly high heat resistance requirements.

[0005] Japanese Patent Application Laid-Open No. 06-324490, Japanese Patent Application Laid-Open No. 2019-66791

[0006] Therefore, an object of the present invention is to improve the above problems of the prior art and provide a reactive polycarboxylic acid resin having good developing characteristics while having both heat resistance and substrate adhesion, and an active energy ray-curable resin composition containing the same.

[0007] As a result of diligent research, the inventors discovered that a resin composition using a reaction product of a specific epoxy resin with an unsaturated group-containing carboxylic acid and a polybasic acid anhydride solves the aforementioned problems, and thus arrived at the present invention.

[0008] In other words, the present invention relates to the following: [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 polymerizable ethylenically unsaturated groups and carboxyl groups in one molecule, and then reacting the reactive epoxycarboxylate compound (c) with a polybasic acid anhydride (d).

[0009]

[0010] (In the formula, n represents the average value and is a number from 1 to 15.) [2] An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [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) and / or a curing agent (D). [4] The active energy ray curable resin composition according to [2] or [3], wherein the reactive compound (B) is at least one compound selected from (meth)acrylate compounds, maleimide compounds, and vinyl compounds, and the curing agent (D) is at least one compound selected from epoxy compounds and oxazine compounds. [5] The active energy ray curable resin composition according to any one of [2] to [4], comprising a photopolymerization initiator (C). [6] An active energy ray curable resin composition according to any one of [2] to [5], further comprising a curing accelerator, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, an isocyanate resin, a polyamide resin, a cyanate ester resin, a polyimide resin, polybutadiene and a modified thereof, polystyrene and a modified thereof, polyethylene and a modified thereof, and a benzoxazine compound. [7] An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1], which is a molding material. [8] An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1], which is a film-forming material. [9] An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1], which is a resist material composition.

[10] A cured product of an active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1].

[11] An article overcoated with a cured product of an active energy ray curable resin composition described in

[10] .

[12] A printed circuit board comprising at least one of a surface protective film and an interlayer insulating film formed by an active energy ray curable resin composition according to any one of items [2] to [9].

[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 combines heat resistance and substrate adhesion.

[0012] Preferably, it can be used in applications such as solder resists for printed circuit boards requiring particularly high insulation reliability, protective films for multilayer printed circuit boards, interlayer insulating materials for multilayer printed circuit boards, solder resists for flexible printed circuit boards, plating resists, and photosensitive optical waveguides.

[0013] 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) 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).

[0014]

[0015] (In general formula (1), n ​​represents the average value and is a number between 1 and 15.)

[0016] First, we will explain the carboxylation step for obtaining the reactive epoxy carboxylate compound (c).

[0017] The epoxy resin (a) represented by general formula (1) can be manufactured, for example, by following the method described in Japanese Patent Application Publication No. 2024-32034.

[0018] 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.

[0019] 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 which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having one hydroxyl group per molecule, semi-esters which are equimolar reaction products of saturated or unsaturated dibasic acids with monoglycidyl (meth)acrylate derivatives, and other monocarboxylic acid compounds containing one carboxyl group per molecule, as well as semi-esters which are equimolar reaction products of saturated or unsaturated dibasic acids with monoglycidyl (meth)acrylate derivatives, and polycarboxylic acid compounds having multiple carboxyl groups per molecule, such as semi-esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having multiple hydroxyl groups per molecule, and semi-esters which are equimolar reaction products of saturated or unsaturated dibasic acids with glycidyl (meth)acrylate derivatives having multiple epoxy groups. Among these, (meth)acrylic acid is preferred.

[0020] 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 the 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, (meth)acrylic acid, the reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid are used.

[0021] The ratio of epoxy resin (a) to carboxylic acid compound (b) in this carboxylation reaction should be appropriately adjusted 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.

[0022] 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).

[0023] 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.

[0024] 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).

[0025] 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.

[0026] 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 so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0031] 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.

[0032] 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 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.

[0033] 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.

[0034] The carboxylation reaction is terminated when the acid value of the sample reaches 5 mg / g or less, preferably 3 mg / g or less, while sampling is performed as needed.

[0035] The preferred molecular weight range for the reactive epoxy carboxylate compound (c) 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.

[0036] 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.

[0037] 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). The reason for introducing a carboxyl group is, for example, to impart solubility in alkaline water to areas not irradiated with active energy rays, or to impart adhesion to metals, inorganic materials, etc., in applications requiring resist patterning. Specifically, a carboxyl group is introduced via an ester bond by adding a polybasic acid anhydride (d) to the hydroxyl group produced by the carboxylation reaction.

[0038] Specific examples of polybasic acid anhydride (d) include, for example, any compound having an acid anhydride structure in one molecule can be used, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, trimellitic anhydride, or maleic anhydride are particularly preferred due to their excellent alkaline aqueous solution developability, heat resistance, hydrolysis resistance, etc.

[0039] The reaction to add polybasic acid anhydride (d) can be carried out by adding polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added should be appropriately adjusted depending on the application.

[0040] When adding the polybasic acid anhydride (d), for example, when the reactive polycarboxylic acid compound (A) of the present invention is 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 30 to 120 mg·KOH / g, more preferably 40 to 110 mg·KOH / 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 has good patterning properties and a wide control range against overdevelopment, and no excessive acid anhydride remains.

[0041] During the reaction, it is preferable to use a catalyst to accelerate the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass based on the total amount of the reactants, that is, the reactive epoxy carboxylate compound (c) obtained from the epoxy compound (a) and the carboxylic acid compound (b), the polybasic acid anhydride (d), 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.

[0042] This acid addition reaction can be carried out without a solvent or by diluting with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for 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 those that can be used in the carboxylation reaction.

[0043] Although the preferred amount of the solvent used should be appropriately adjusted according to the viscosity of the resulting resin and its use, it is preferably used so as to be 70 to 20% by mass, more preferably 60 to 30% by mass, based on the solid content.

[0044] 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 utilized as the composition.

[0045] Further, it is preferable to use the same heat polymerization inhibitor and the like as those exemplified in the carboxylation reaction.

[0046] This acid addition reaction is terminated at the point where the acid value of the reaction product is within the range of plus or minus 10% of the set acid value while appropriately sampling.

[0047] The preferred 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 1000 to 10,000.

[0048] When it is smaller than this molecular weight, 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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 of the ε-caprolactone adduct of hydroxyvivariate neopeneglycol, poly(meth)acrylate of the reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate and its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate and its ethylene oxide adduct, and the like.

[0053] The radical-reactive maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimoidhexanoic acid, 4-maleimoidbutyric acid, bis(4-maleimoidphenyl)methane, 2,2-bis{4-(4-maleimoidphenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, and bis(3,5-dimethyl-4- Maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4 -Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1,5-bismaleimidepentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimidehexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis (maleimidomethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,Examples include 5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, etc.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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).

[0060] 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. Examples of other components that can be used are listed below.

[0061] As the photopolymerization initiator (C), radical-type photopolymerization initiators and cationic photopolymerization initiators are preferred. 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-chloroanthra 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.

[0062] 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.

[0063] 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., Cyracure UVI-6990 manufactured by UnionCarbide Inc.) and triphenylsulfonium hexafluoroantimonate (e.g., Cyracure UVI-6974 manufactured by UnionCarbide Inc.). Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate.

[0064] 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., Sandray 1000 from Sandoz), and α,α,α-tribromomethylphenyl sulfone (e.g., BMPS from Iron & Steel Chemical Co., Ltd.). Triazine 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), and 2,4-trichloromethyl-(piperonyl)-6-triazine (Panc Examples include Triazine PP (manufactured by Him Co., Ltd.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B (manufactured by Panchim Co., Ltd.), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd., etc.), and 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

[0065] 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 Irgacure 261 from CibaGeigy), and bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridine-1-yl)phenyl]titanium (such as CGI-784 from CibaGeigy).

[0066] 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.

[0067] Of these, considering the properties of the reactive polycarboxylic acid compound (A) of the present invention, a radical-type photopolymerization initiator is particularly preferred.

[0068] Furthermore, the active energy ray curable resin composition of the present invention may contain coloring pigments. Examples of coloring pigments include organic pigments such as phthalocyanine-based, azo-based, and quinacridone-based pigments, and inorganic pigments such as carbon black and titanium dioxide. Of these, carbon black is most preferred due to its high dispersibility. Pigments 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 carbon black.

[0069] 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, and antioxidants.

[0070] 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.

[0071] The active energy ray-curable resin composition of the present invention may use a curing agent (D) as needed. In particular, when using a reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use resins that do not react to active energy rays, such as well-known epoxy resins or oxazine compounds. This is because carboxyl groups derived from the reactive polycarboxylic acid compound (A) remain even after reaction and curing with active energy rays, 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 crosslinked structure. The well-known epoxy resin can be the cationic reactive monomer mentioned above. Specific examples of oxazine compounds include, for example, B-m type benzoxazine, P-a type benzoxazine, and B-a type benzoxazine (all manufactured by Shikoku Chemicals, Inc.).

[0072] 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, in order to adjust the viscosity.

[0073] 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.

[0074] In the present invention, "molding material" refers to a material used in which an uncured composition is placed in a mold, or a mold is pressed onto an object to form it, and then a curing reaction is induced by active energy rays to form the object, or an uncured composition is irradiated with focused light such as a laser to induce a curing reaction and form the object.

[0075] Specific applications include flat-formed sheets, encapsulating materials for protecting elements, so-called nanoimprint materials where a microfabricated "mold" is pressed onto an uncured composition for fine molding, and peripheral encapsulating materials for light-emitting diodes, photoelectric conversion elements, and other devices with particularly stringent thermal requirements.

[0076] In this invention, film-forming materials are those used for the purpose of coating the surface of a substrate. Specific applications include ink materials such as gravure inks, flexographic inks, silkscreen inks, and offset inks; coating materials such as hard coats, top coats, overprint varnishes, and clear coats; adhesive materials such as various adhesives and tacks for lamination, optical discs, etc.; and resist materials such as solder resists, etching resists, and micromachine resists. Furthermore, so-called dry films, which are formed by temporarily coating a film-forming material onto a releaseable substrate and then laminating them onto the intended substrate to form a film, also fall under the category of film-forming materials.

[0077] Among these, the introduction of a carboxyl group in reactive polycarboxylic acid compound (A) enhances adhesion to the substrate. Therefore, it is also preferable to use reactive polycarboxylic acid compound (A) for coating plastic or metal substrates as an alkaline water-developable resist material composition, taking advantage of its solubility in alkaline aqueous solutions.

[0078] 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.

[0079] Particularly suitable applications include a wide range of applications requiring resin compositions, such as photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, interlayer insulating materials for build-up methods, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component embedding resins, color resists, color filters, black matrices, and even optical waveguides and other optoelectronic substrates and optical substrates.

[0080] Furthermore, it can be suitably used in resin compositions for insulating layers of multilayer printed circuit boards (multilayer printed circuit boards with a cured photosensitive resin composition as the insulating layer), resin compositions for interlayer insulating layers (multilayer printed circuit boards with 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).

[0081] It is particularly suitable for use in dry film applications where mechanical strength is required before the curing reaction by energy rays.

[0082] 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.

[0083] 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, and also includes multilayer materials having a layer of said cured product.

[0084] 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, or spin coating, and the coating film is 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.

[0085] 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.

[0086] 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 %.

[0087] 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 were as follows. • GPC used in Synthesis Example 1: Instrument: Waters Column: SHODEX GPC KF-601, KF-602, KF-602.5, KF-603 Eluent: THF (tetrahydrofuran); 0.3 ml / min, 40°C Detector: RI (differential refractive detector) • GPC used in Example 1: Instrument: TOSOH HLC-8220GPC Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C Detector: RI (differential refractometer) Molecular weight standard: Polystyrene

[0088] (Synthesis Example 1): Synthesis of phenolic resin In a flask equipped with a reflux condenser and a stirrer, 254 parts by mass of phenol, 63 parts by mass of water, and 27 parts by mass of sodium hydroxide were charged, stirred, dissolved, and heated to 110°C. 44 parts by mass of furfural were then added dropwise over 2 hours. The mixture was then reacted at 110°C for 3 hours, and then the temperature was raised to 145°C. During the heating process, the water that distilled out was removed from the system. After reaching 145°C, the mixture was reacted for 4 hours. The mixture was then cooled to 80°C, 63 parts by mass of water was added, and neutralization was performed by adding 4 parts by mass of phosphoric acid and 63 parts by mass of 35% hydrochloric acid. After repeated washing with water, the unreacted phenol was removed by distillation under reduced pressure to obtain 109 parts by mass of phenolic resin. To 78 parts by mass of the obtained phenol resin, 254 parts by mass of epichlorohydrin (ECH, the same applies hereafter), 64 parts by mass of dimethyl sulfoxide (DMSO, the same applies hereafter), and 13 parts by mass of water were charged into a reaction vessel. After heating, stirring, and dissolution, 23 parts by mass of flake sodium hydroxide were added in installments over 2 hours while maintaining the temperature at 45°C. The reaction was then carried out further at 45°C for 2 hours and at 70°C for 60 minutes. After repeated washing with water to remove the by-product salts and dimethyl sulfoxide, excess ECH was distilled off from the oil layer under reduced pressure, and 218 parts by mass of methyl isobutyl ketone was added to the residue and dissolved. This methyl isobutyl ketone solution was heated to 70°C, 7 parts by mass of a 30% aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. After that, the reaction solution was washed with water repeatedly until the washing solution became neutral. Finally, 97 parts by mass of epoxy resin represented by formula (1) was obtained by distilling off the methyl isobutyl ketone from the oil layer under reduced pressure. The epoxy equivalent was 214 g / eq., the softening point was 49°C, the ICI melt viscosity was 0.04 Pa·s, and the average repeating unit n from GPC was 2.1.

[0089] (Example 1): Synthesis of reactive polycarboxylic acid compound (A) 42.2 g of epoxy resin (a) obtained in Synthesis Example 1 and 14.8 g of acrylic acid (AA) as carboxylic acid compound (b) were added. 0.24 g of triphenylphosphine as catalyst, 0.24 g of BHT as polymerization inhibitor, and diethylene glycol monoethyl ether acetate as solvent were added to a solid content of 70% by mass. The mixture was reacted at 100°C for 24 hours to obtain a reactive epoxy acrylate resin (c) solution. To the obtained reactive epoxy carboxylate compound (c) solution, 20.6 g of THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as polybasic acid anhydride (d) and diethylene glycol monoethyl ether acetate as solvent were added to a solid content of 65%. An acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A) solution with a solid content acid value of 106.6 mg・KOH / g. The solid content acid value (mg・KOH / g) was measured in solution and then converted to a value based on solid content.

[0090] (Example 2 and Comparative Examples 2-1, 2-2): Preparation and evaluation of the resin composition. Components (A) to (D) in the amounts (parts by mass) shown in Table 1, a thermosetting catalyst, and a solvent were blended and then uniformly dispersed using a stirring device to obtain a photosensitive resin composition.

[0091] Each item of the evaluation criteria will be described in detail.

[0092] Developability Evaluation (abbreviated as "developability" in the table): A photosensitive resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 20 μm using an applicator, and the coating was dried in a hot air dryer at 80°C for 30 minutes. Then, spray development was performed with a 1% sodium carbonate aqueous solution (spray pressure 0.2 MPa), and the time until the coating was completely dissolved, the so-called break time, was used to evaluate the developability (unit: seconds).

[0093] Glass transition temperature evaluation (abbreviated as Tg 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 20 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 material was irradiated with ultraviolet light. After curing in a 150°C oven for 1 hour, the copper foil was removed with iron(III) chloride 45° Baume (manufactured by Junsei Chemical Co., Ltd.) to obtain the cured product. DMA measurement (TA Instruments: RSA-G2) was performed on the prepared cured product to determine the temperature at which tangentδ was maximized (unit: °C).

[0094] 90° Peel Strength Evaluation (Abbreviation in Table: Adhesion) A photosensitive resin composition was applied to the rough surface of rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 20 μm using an applicator, and the coating was dried in a hot air dryer at 80°C for 30 minutes. After that, 500 mJ / cm² was applied using an ultraviolet irradiator (GS YUASA: CS 30L-1). ２ The copper foil was irradiated with ultraviolet light and cured in a 150°C oven for 1 hour. A two-part epoxy adhesive (ThreeBond 2081D) was applied to the resin of the resulting resin-coated copper foil, and it was bonded to a copper-clad laminate ELC-4762 (Sumitomo Bakelite Co., Ltd.) as a support. After cutting the resulting laminate to a width of 2 cm, a test specimen was prepared by cutting and removing the rolled copper foil so that a width of 1 cm remained. The obtained test specimen was set in a 90-degree peel strength measuring device (Shimadzu Corporation, Autograph AGS-X), and peeling was performed under the condition of a peel test tensile speed of 50 mm / min to evaluate the peel strength (unit: N / mm).

[0095]

[0096] Note *1 Nippon Kayaku Co., Ltd.: Bisphenol A type acid-modified epoxy acrylate (solid content acid value 98 mg KOH / g) *2 Nippon Kayaku Co., Ltd.: Bisphenol F type acid-modified epoxy acrylate (solid content acid value 98 mg KOH / g) *3 Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate *4 IGM Resins B. V.: 2-methyl-(4-(methylthio)phenyl)-2-morpholinopropan-1-one *5 Nippon Kayaku Co., Ltd.: 2,4-diethylthioxanthone *6 Nippon Steel Chemical & Material Co., Ltd.: Bisphenol A type epoxy resin *7 Hokko Chemical Industry Co., Ltd.: Triphenylphosphine *8 Shinko Organic Chemical Industry Co., Ltd.: Diethylene glycol monoethyl ether acetate

[0097] Based on the above results, it can be said that the active energy ray curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has higher Tg and adhesion, as well as superior developability, compared to the comparative resin composition.

[0098] <Curing Test> [Example A-1] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 11 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 0.15 parts of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 10 parts of KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type phenol resin), 10 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 1.5 parts of BA-BXZ (manufactured by Konishi Chemical Co., Ltd., bisphenol A type benzoxazine), and 16 parts of acetone as a solvent were mixed together, and a cured product was obtained by heating at 130°C for 10 minutes and at 200°C for 1 hour under a nitrogen atmosphere.

[0099] [Example A-2] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 21 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 3 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 10 parts of CYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd., bisphenol A type cyanate resin), 0.2 parts of TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.002 parts of Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), 0.001 parts of San-Aid SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), and 20 parts of acetone as a solvent were mixed together, and a cured product was obtained by heating at 130°C for 10 minutes and then at 200°C for 1 hour under a nitrogen atmosphere.

[0100] [Example A-3] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 45 parts of the compound (B-1) obtained in Synthesis Example 2-1, 16 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 0.16 parts of HPC-8000 (manufactured by DIC Corporation, active ester) 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals, Ltd., curing accelerator), and 6.7 parts of toluene as a solvent were mixed together, and a cured product was obtained by heating under a nitrogen atmosphere at 130°C for 10 minutes and then at 200°C for 1 hour.

[0101] [Example A-4] A mixture was prepared by combining 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 45 parts of the compound (B-1) obtained in Synthesis Example 2-1, 14.5 parts of RE-305 (liquid epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), 14.5 parts of KAYAHARD A-A (amine compound, manufactured by Nippon Kayaku Co., Ltd.), 14.5 parts of KAYAHARD MCD (acid anhydride compound, manufactured by Nippon Kayaku Co., Ltd.), 0.15 parts of 2E4MZ:2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Chemicals, Inc.), and 20 parts of acetone as a solvent. The mixture was heated under a nitrogen atmosphere at 130°C for 10 minutes and then at 200°C for 1 hour to obtain a cured product.

[0102] [Example A-5] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 45 parts of the compound (B-1) obtained in Synthesis Example 2-1, 0.6 parts of phenylmaleimide (manufactured by Tokyo Chemical Industries, a maleimide compound), 32.5 parts of OPE-2st 2200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound), 21.5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., a compound having an ethylenically unsaturated bond), and KAYARAD A mixture containing 0.6 parts of R-684 (manufactured by Nippon Kayaku Co., Ltd., a compound having an ethylenically unsaturated bond), 0.6 parts of acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., a compound having an ethylenically unsaturated bond), 2 parts of TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, an allyl compound), and 0.3 parts of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., a polymerization initiator) was prepared and heated under a nitrogen atmosphere at 130°C for 10 minutes and then at 200°C for 1 hour to obtain a cured product.

[0103] [Example A-6] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 45 parts of the compound (B-1) obtained in Synthesis Example 2-1, 2.2 parts of MIZ-001 (maleimide compound, manufactured by Nippon Kayaku Co., Ltd.), 41.2 parts of OPE-2st 2200 (polyphenylene ether compound, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 13.5 parts of STR-2000 (compound having an ethylenically unsaturated bond, manufactured by Nippon Kayaku Co., Ltd.), 8.2 parts of the polyimide compound obtained by the method described in WO2023 / 013224A1, 13 parts of Septon 2104 (polystyrene modified product, manufactured by Kuraray Co., Ltd.), and 0.3 parts of DCP: dicumyl peroxide (polymerization initiator, manufactured by Kayaku Nourion Co., Ltd.) were mixed together, and a cured product was obtained by heating at 130°C for 10 minutes and at 200°C for 1 hour under a nitrogen atmosphere.

[0104] [Example A-7] 15 parts of the reactive polycarboxylic acid compound (A) obtained in Example 1, 10 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type epoxy resin), 15 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 7.5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 10 parts of KAYARAD ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type acid-modified epoxy acrylate resin), 25 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), Irgacure Mix 0.5 parts of 290 (a polymerization initiator manufactured by BASF) and 25 parts of cyclopentanone, and apply the mixture to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 50 μm. Dry the coating in a hot air dryer at 130°C for 10 minutes, and then irradiate with 500 mJ / cm using an ultraviolet irradiator (GS YUASA: CS 30L-1). ２ We were able to obtain a cured product by irradiating it with ultraviolet light using this energy.

[0105] DMA measurements (TA Instruments: RSA-G2) were performed on the cured products obtained in Examples A-1 to A-7, and the temperature at which tangentδ was maximized was determined (abbreviated as Tg in the table, unit: °C). In addition, the cured product was cut into 4 mm squares, 1.0 to 5.0 mg was weighed into a measuring pan, and the 5% weight loss rate was measured under conditions of an air flow rate of 100 mL / sec and a heating rate of 10 °C / min (abbreviated as Td5 in the table, unit: °C). A TGA / DSC1 (METTLER TOLEDO) can be used as the measuring device.

Claims

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 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). (In the formula, n represents the average value and is a number between 1 and 15.) 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 at least one selected from a reactive compound (B) other than the reactive polycarboxylic acid compound (A) and a curing agent (D).

4. The active energy ray curable resin composition according to claim 2 or 3, wherein the reactive compound (B) is at least one compound selected from (meth)acrylate compounds, maleimide compounds, and vinyl compounds, and the curing agent (D) is at least one compound selected from epoxy compounds and oxazine compounds.

5. An active energy ray curable resin composition according to any one of claims 2 to 4, comprising a photopolymerization initiator (C).

6. The active energy ray curable resin composition according to any one of claims 2 to 5, further comprising a curing accelerator, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, an isocyanate resin, a polyamide resin, a cyanate ester resin, a polyimide resin, polybutadiene and modified thereof, polystyrene and modified thereof, polyethylene and modified thereof, and a benzoxazine compound.

7. An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in claim 1, which is a molding material.

8. An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) described in claim 1, which is a film-forming material.

9. An active energy ray curable resin composition comprising the reactive polycarboxylic acid compound (A) according to claim 1, which is a resist material composition.

10. A cured product of an active energy ray curable resin composition containing the reactive polycarboxylic acid compound (A) described in claim 1.

11. An article overcoated with a cured product of the active energy ray curable resin composition described in claim 10.

12. A printed circuit board comprising at least one of a surface protective film and an interlayer insulating film formed by the active energy ray curable resin composition according to any one of claims 2 to 9.

Images