JP7567352B2 - (Meth)acrylate resin, curable resin composition, cured product and article - Google Patents

Description

The present invention relates to a (meth)acrylate resin capable of forming a cured product having excellent elongation and dielectric properties, a curable resin composition containing the same, a cured product of the curable resin composition, and a resist member.

In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical components, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surface of various substrates, has excellent curing properties, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding materials that can form a cured coating film that has properties such as elongation, low dielectric constant, and low dielectric tangent of the obtained cured product.

A known conventional active energy ray-curable composition is a photosensitive resin composition containing an epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride (see, for example, Patent Document 1). However, there are problems with this composition, such as insufficient elongation in the cured product and insufficient dielectric properties, such as an increase in the dielectric constant and dielectric loss tangent due to the generation of hydroxyl groups.

Therefore, there was a demand for a material that had excellent dielectric properties in addition to ductility.

Japanese Patent Application Publication No. 8-259663

The problem that the present invention aims to solve is to provide a (meth)acrylate resin capable of forming a cured product having excellent elongation and dielectric properties, a curable resin composition containing the same, and a cured product and article of the curable resin composition.

As a result of intensive research into solving the above problems, the present inventors discovered that the above problems could be solved by using an epoxy resin that uses as essential raw materials a compound having a phenolic hydroxyl group, an aromatic compound having at least two ethylenically unsaturated bonds, and epihalohydrin, and a (meth)acrylate resin that uses as essential raw materials an unsaturated monobasic acid, and thus completed the present invention.

That is, the present invention relates to a (meth)acrylate resin having, as essential raw materials, an epoxy resin (A) and an unsaturated monobasic acid (B), characterized in that the epoxy resin (A) has, as essential raw materials, a compound (a1) having a phenolic hydroxyl group, an aromatic compound (a2) having at least two ethylenically unsaturated bonds, and an epihalohydrin (a3), a curable resin composition containing the same, and a cured product and article of the curable resin composition.

The (meth)acrylate resin of the present invention can form a cured product having excellent elongation and dielectric properties, so that a curable resin composition containing the (meth)acrylate resin and a photopolymerization initiator can be used as a coating agent or adhesive, and is particularly suitable for use as a coating agent.

The (meth)acrylate resin of the present invention is characterized in that it contains an epoxy resin (A) and an unsaturated monobasic acid (B) as essential raw materials.

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Furthermore, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The epoxy resin (A) used is one whose essential raw materials are a compound (a1) having a phenolic hydroxyl group, an aromatic compound (a2) having at least two ethylenically unsaturated bonds, and epihalohydrin (a3).

The compound (a1) having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (1-1) to (1-4).

In the above structural formulas (1-1) to (1-4), R ¹ is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and R ² is each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and for example, in the naphthalene ring of structural formula (1-2), it may be substituted on any ring, in structural formula (1-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (1-4), it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is p and q.

As the compound having a phenolic hydroxyl group, for example, a reaction product in which a compound having one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) are used as essential reaction raw materials can also be used. In addition, a novolac-type phenolic resin in which one or more compounds having at least one phenolic hydroxyl group in the molecule are used as reaction raw materials can also be used.

[In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer from 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is each independently any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (x-5), Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer from 1 to 4.]

These compounds (a1) having a phenolic hydroxyl group can be used alone or in combination of two or more.

The aromatic compound (a2) used has at least two ethylenically unsaturated bonds. Examples include aromatic divinyl compounds such as divinylbenzene, alkyl divinylbenzene, diallyl phthalate, and diisopropenylbenzene, and aliphatic divinyl compounds such as glycerol diallyl ether and trimethylolpropane triacrylate. These aromatic compounds (a2) can be used alone or in combination of two or more. In addition, aromatic divinyl compounds are preferred because they can produce (meth)acrylate resins that can form cured products with excellent elongation and dielectric properties, and among these, divinylbenzene and diisopropenylbenzene are particularly preferred.

Examples of the divinylbenzene include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. These divinylbenzenes can be used alone or in combination of two or more.

Examples of the diisopropenylbenzene include 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene. These diisopropenylbenzenes can be used alone or in combination of two or more.

The aromatic compound (a2) may be used in combination with other reactive third components as necessary. Examples of the reactive third components include aromatic monovinyl compounds such as styrene, methylstyrene, ethylstyrene, and monobromostyrene, and aliphatic monovinyl compounds such as (meth)acrylic acid methyl ester, (meth)acrylic acid stearyl ester, (meth)acrylic acid, N-methylol (meth)acrylamide, and γ-mercaptopropyltrimethoxysilane. These reactive third components may be used alone or in combination of two or more.

The amount of the aromatic compound (a2) used is preferably in the range of 0.25 to 1 mole of the aromatic compound (a2) per mole of the compound (a1) having a phenolic hydroxyl group, since this produces a (meth)acrylate resin capable of forming a cured product having excellent elongation and dielectric properties.

Examples of the epihalohydrin (a3) include epichlorohydrin, epibromohydrin, and the like. These epihalohydrins can be used alone or in combination of two or more. Among these, epichlorohydrin is preferred because the reaction is easy to control.

In addition, the (meth)acrylate resin of the present invention is preferably one represented by the following structure, since it is capable of forming a cured product having excellent elongation and dielectric properties.

[In formula (2), each ring A is independently a benzene ring or a naphthalene ring; each R ¹ is independently a hydrogen atom, a methyl group, an ethyl group, or a propyl group; each R ² is independently a hydrogen atom, a methyl group, an ethyl group, or a propyl group; each X is independently a glycidyl group or one represented by the following structural formula (X-1); m is an integer from 1 to 6; and n is an integer from 1 to 20. At least one of Xs is represented by the following structural formula (X-1).]

[In formula (X-1), R ² is a hydrogen atom or a methyl group.]

The method for producing the epoxy resin (A) is not particularly limited, and it can be produced by any known method. For example, it may be produced by a method in which all of the reaction raw materials are reacted at once, or by a method in which the reaction raw materials are reacted sequentially.

As a method for reacting the reaction raw materials sequentially, for example, the compound (a1) having a phenolic hydroxyl group and the aromatic compound (a2) are reacted in the presence of an acid catalyst at a temperature range of 80 to 200°C, and then 1 to 10 moles of the epihalohydrin (a3) are added per mole of hydroxyl group contained in the reaction product of the compound (a1) having a phenolic hydroxyl group and the aromatic compound (a2), and further, 0.9 to 10 moles of a basic catalyst per mole of hydroxyl group of the raw material are added all at once or gradually while reacting at a temperature of 20 to 120°C for 0.5 to 10 hours to perform an epoxidation reaction. The basic catalyst may be a solid or an aqueous solution thereof. When an aqueous solution is used, it may be added continuously, and water and epihalohydrin may be continuously distilled from the reaction mixture under reduced pressure or normal pressure, and further separated to remove water and continuously return epihalohydrin to the reaction mixture.

The reaction of the compound (a1) having a phenolic hydroxyl group, the aromatic compound (a2), and the epihalohydrin (a3) can also be carried out in an organic solvent, if necessary.

In industrial production, all of the epihalohydrin used in the first batch of epoxy resin production is new, but from the next batch onwards, it is preferable to use epihalohydrin recovered from the crude reaction product in combination with new epihalohydrin equivalent to the amount consumed and lost in the reaction. In this case, it may contain impurities such as glycidol that are derived from the reaction of epichlorohydrin with water, organic solvents, etc.

The obtained epoxy resin (A) is washed with water as necessary, and unreacted epihalohydrin and the organic solvent used are removed by distillation under reduced pressure with heating. In order to obtain an epoxy resin with even less hydrolyzable halogen, the obtained epoxy resin (A) can be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to further react. In this case, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present in order to improve the reaction rate. When the phase transfer catalyst is used, the amount of the catalyst used is preferably in the range of 0.1 to 3 mass% based on the epoxy resin used. After the reaction is completed, the salt formed is removed by filtration, washing with water, or the like, and the solvent such as toluene or methyl isobutyl ketone is further removed by distillation under reduced pressure with heating to obtain a high-purity epoxy resin (A).

In particular, when reacting the reaction product of the compound (a1) having a phenolic hydroxyl group and the aromatic compound (a2) with epihalohydrin (a3), the water concentration in the solvent is set to 5 to 25%, making it possible to efficiently obtain the desired epoxy resin.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. In addition, solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acid catalysts can be used alone or in combination of two or more.

Examples of commercially available solid acid catalysts include "Amberlyst 15DRY", "Amberlyst 15JWET", "Amberlyst 16WET", "Amberlyst 35WET", and "Amberlyst 33" manufactured by Organo Corporation, and "Teikacure-6", "Teikacure-10", and "Teikacure-15" manufactured by Teika Corporation.

Examples of the basic catalyst include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; trioctylmethylammonium chloride, ... Examples of the quaternary ammonium salts include octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. In particular, alkali metal hydroxides are preferred because they have excellent catalytic activity in the epoxy resin synthesis reaction, and for example, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts can be used alone or in combination of two or more. When using the basic catalyst, it may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or in the form of a solid.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. In addition, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

In addition, in the production of the epoxy resin (A), a compound having a phenolic hydroxyl group other than the compound (a1) having a phenolic hydroxyl group can be used in combination, as long as the effects of the present invention are not impaired.

Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (1) can also be used.

［式（３）中、Ｘは、炭素数１～１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、又は（ポリ）カーボネート鎖を表し、構造中にハロゲン原子やアルコキシ基等を有していても良い。Ｙは、水素原子又はメチル基である。］

[In formula (3), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

Examples of the polyoxyalkylene chain include polyoxyethylene chains and polyoxypropylene chains.

The (poly)ester chain may be, for example, a (poly)ester chain represented by the following structural formula (X-1).

［式（４）中、Ｒ^１は、炭素原子数１～１０のアルキレン基であり、ｎは１～５の整数である。］

[In formula (4), R ¹ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

These unsaturated monobasic acids (B) can be used alone or in combination of two or more.

The amount of the unsaturated monobasic acid (B) used is preferably in the range of 0.2 to 0.8 moles of acid groups in the unsaturated monobasic acid (B) per mole of epoxy groups in the epoxy resin (A), and more preferably in the range of 0.25 to 0.75 moles, since the resulting (meth)acrylate resin has epoxy groups and (meth)acryloyl groups and exhibits excellent elongation and dielectric properties.

The method for producing the (meth)acrylate resin of the present invention is not particularly limited, and the resin can be produced by any known method. For example, a method in which all of the reaction raw materials containing the epoxy resin (A) and the unsaturated monobasic acid (B) are reacted together in the presence of an acidic or basic catalyst at a temperature range of 70 to 140°C is preferred.

The reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) can also be carried out in an organic solvent, if necessary.

The acid catalyst may be the same as those exemplified above, and the acid catalyst may be used alone or in combination of two or more.

As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more kinds. Among these, phosphine compounds are preferred because they can give a (meth)acrylate resin capable of forming a cured product having excellent elongation and dielectric properties.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

In the production of the (meth)acrylate resin of the present invention, a polymerization inhibitor, an antioxidant, etc. can also be used as necessary.

Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, and N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, and other amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl= Thioether compounds such as 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N- Nitroso compounds such as nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol; triphenyl phosphite; 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; trisnonylphenyl phosphite; and (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl phosphite. Examples of the polymerization inhibitor include phosphate compounds such as esters, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, and zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and 3,3'-thiodipropionate distearyl. These polymerization inhibitors can be used alone or in combination of two or more.

The antioxidant may be the same as the compounds exemplified as the polymerization inhibitor, and the antioxidant may be used alone or in combination of two or more kinds.

In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

The (meth)acrylate resin of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

Examples of commercially available photopolymerization initiators include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", "Omnirad 81" (IGM) Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (Stoffa Chemical Co.); "Trigonal P1" (Akzo Nobel Co., Ltd.), "SANDORAY 1000" (SANDOZ Co., Ltd.); "DEAP" (Upjohn Chemical Co., Ltd.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (Ward Blenkinsop Co., Ltd.); "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the curable resin composition.

The curable resin composition of the present invention may contain resin components other than the (meth)acrylate resin described above (hereinafter, sometimes referred to as "other resin components"). Examples of the other resin components include epoxy resins, resins having polymerizable unsaturated groups, various (meth)acrylate monomers, etc.

The epoxy resin may be the same as those exemplified above as epoxy resin (A), and the epoxy resin may be used alone or in combination of two or more kinds.

The resin having a polymerizable unsaturated group may be any resin having a polymerizable unsaturated group in the resin, and examples thereof include epoxy resins having a polymerizable unsaturated group, urethane resins having a polymerizable unsaturated group, acrylic resins having a polymerizable unsaturated group, amide-imide resins having a polymerizable unsaturated group, acrylamide resins having a polymerizable unsaturated group, and ester resins having a polymerizable unsaturated group.

Examples of the epoxy resin having a polymerizable unsaturated group include an epoxy (meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, with a polybasic acid anhydride, and an epoxy (meth)acrylate resin having a urethane group obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group and, if necessary, with a polybasic acid anhydride.

The epoxy resin may be the same as those exemplified above as epoxy resin (A), and the epoxy resin may be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified as the unsaturated monobasic acid (B) described above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

Examples of the aliphatic polybasic acid anhydrides include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,2,3,4-butanetetracarboxylic acid. In addition, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid.

These polybasic acid anhydrides can be used alone or in combination of two or more.

Examples of the polyisocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (5); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more types.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（５）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１～３の整数であり、ｍは１～１５の整数である。］

[In the formula, R ¹ is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is independently either an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural portion represented by structural formula (5) via a methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

The method for producing the epoxy resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the urethane resin having a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polyol compound and a polybasic acid anhydride.

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced into the molecular structure of the various polyol compounds; lactone modified compounds in which (poly)lactone structures have been introduced into the molecular structure of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds can be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

The method for producing the urethane resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acrylic resin having a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component, and then reacting the acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product as necessary.

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

The method for producing the acrylic resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The amide-imide resin having a polymerizable unsaturated group may be, for example, one obtained by reacting an amide-imide resin having an acid group and/or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and/or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, it is preferable that the resin has an acid anhydride group, and it is more preferable that the resin has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mg KOH/g measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value under conditions in which the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mg KOH/g.

The amide-imide resin can be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride.

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

In addition, if necessary, the amide-imide resin can be used in combination with a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the (meth)acrylate compound having an epoxy group include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more.

The method for producing the amide-imide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acrylamide resin having a polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

As the compound having a phenolic hydroxyl group, the same compounds as those exemplified as the compound (a1) having a phenolic hydroxyl group described above can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it gives a curable resin composition capable of forming a cured product having excellent elongation and dielectric properties. The alkylene oxides can be used alone or in combination of two or more kinds.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can produce a curable resin composition capable of forming a cured product having excellent elongation and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more kinds.

Examples of the N-alkoxyalkyl (meth)acrylamide compounds include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, and N-butoxyethyl (meth)acrylamide. The N-alkoxyalkyl (meth)acrylamide compounds can be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The method for producing the acrylamide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The acid catalyst may be the same as those exemplified above, and the acid catalyst may be used alone or in combination of two or more.

Examples of the ester resin having a polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

The compound having a phenolic hydroxyl group may be the same as the compounds exemplified above as compounds having a phenolic hydroxyl group, and the compound having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

As the alkylene oxide, the same alkylene oxides as those exemplified above can be used. Among these, ethylene oxide or propylene oxide is preferred because it gives a curable resin composition capable of forming a cured product having excellent elongation and dielectric properties. The alkylene oxides can be used alone or in combination of two or more kinds.

As the alkylene carbonate, the same ones as those exemplified above as alkylene carbonates can be used. Among these, ethylene carbonate or propylene carbonate is preferred because it gives a curable resin composition capable of forming a cured product having excellent elongation and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

The method for producing the ester resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The acid catalyst may be the same as those exemplified above, and the acid catalyst may be used alone or in combination of two or more.

The amount of the resin having a polymerizable unsaturated group used is preferably in the range of 10 to 900 parts by mass per 100 parts by mass of the (meth)acrylate resin of the present invention.

The various (meth)acrylate monomers are not particularly limited as long as they have a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzoic acid mono(meth)acrylate compounds such as benzoic acid mono(meth)acrylate, benzoic acid mono(meth)acrylate, and benzoic acid mono(meth)acrylate; Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds, such as phenyl(meth)acrylate, phenylbenzyl(meth)acrylate, phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, benzylbenzyl(meth)acrylate, and phenylphenoxyethyl(meth)acrylate: (poly)oxyacrylates in which a polyoxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the various mono(meth)acrylate monomers described above. alkylene-modified mono(meth)acrylate compounds; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds described above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; aliphatic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. cyclic di(meth)acrylate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; the aliphatic tri(meth)acrylate compounds (poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compound; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compound; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, or dipentaerythritol hexa(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, or the like has been introduced into the molecular structure of the above-mentioned aliphatic poly(meth)acrylate compound; (poly)oxyalkylene-modified poly(meth)acrylate compounds having 4 or more functional groups in which a (poly)oxyalkylene chain such as a methylene chain has been introduced; lactone-modified poly(meth)acrylate compounds having 4 or more functional groups in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, (Meth)acrylate compounds having a hydroxyl group, such as erythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (poly)oxyalkylene modified compounds obtained by introducing a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, into the molecular structure of the (meth)acrylate compound having a hydroxyl group; lactone modified compounds obtained by introducing a (poly)lactone structure into the molecular structure of the (meth)acrylate compound having a hydroxyl group; 2-acryloyl (meth)acrylate compounds having an isocyanate group such as 2-methacryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The above-mentioned various (meth)acrylate monomers can be used alone or in combination of two or more kinds.

The curable resin composition of the present invention may also contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler, polymer particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

Examples of the polybasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]hepta Examples of the polybasic acid include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. Examples of the polybasic acid include copolymers of conjugated diene vinyl monomers and acrylonitrile, and polymers having carboxyl groups in the molecule. These polybasic acids can be used alone or in combination of two or more.

The unsaturated monobasic acid may be the same as those exemplified as the unsaturated monobasic acid (B) described above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more kinds.

Examples of the amide-based compounds include dicyandiamide, polyamide resins synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, alkyl peroxycarbonates, etc. These organic peroxides can be used alone or in combination of two or more kinds.

Examples of the polyol compounds include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and mixtures of the polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation reaction of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

The curing accelerator accelerates the curing reaction, and examples of the accelerator include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These accelerators can be used alone or in combination of two or more. The amount of the accelerator added is preferably in the range of 0.01 to 10% by mass based on the solid content of the curable resin composition.

Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc.

The pigment may be any known inorganic or organic pigment.

Examples of the inorganic pigments include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, the amount is preferably in the range of 0.1 to 20% by mass in the total resin composition.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As a source of ultraviolet light, ultraviolet lamps are generally used from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , and more preferably 0.5 to 10 kJ/m ^2. When the cumulative light amount is within the above range, it is preferable because the occurrence of uncured portions can be prevented or suppressed.

The irradiation of the active energy rays may be carried out in one step or in two or more steps.

The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices.

The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the examples listed below.

(Synthesis Example 1: Production of Epoxy Resin (1))
285 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 115°C under a nitrogen atmosphere. 208 parts by mass of 1,4-divinylbenzene were added dropwise over 2 hours, and the mixture was held at 115°C for 5 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution were added, and the toluene was removed at 170°C to obtain a phenolic resin (1). The hydroxyl group equivalent of this phenolic resin (1) was 108 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.8.

Next, 108 parts by mass of phenolic resin (1) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of a 20% aqueous sodium hydroxide solution was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (1). The epoxy equivalent of this epoxy resin (1) was 195 g/equivalent.

(Synthesis Example 2: Production of Epoxy Resin (2))
233 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 115°C under a nitrogen atmosphere. 130 parts by mass of 1,4-divinylbenzene was added dropwise over 2 hours, and the mixture was held at 115°C for 3 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (2). The hydroxyl group equivalent of this phenolic resin (2) was 90 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.5.

Next, 90 parts by mass of phenolic resin (2) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and then 1,000 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (2). The epoxy equivalent of this epoxy resin (2) was 178 g/equivalent.

(Synthesis Example 3: Production of Epoxy Resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 199 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 78 parts by mass of 1,4-divinylbenzene was added dropwise over 2 hours, and the mixture was held at 115°C for 3 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (3). The hydroxyl group equivalent of this phenolic resin (3) was 79 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.3.

Next, 79 parts by mass of phenolic resin (3) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (3). The epoxy equivalent of this epoxy resin (3) was 164 g/equivalent.

(Synthesis Example 4: Production of Epoxy Resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 181 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 52 parts by mass of 1,4-divinylbenzene were added dropwise over 2 hours, and the mixture was held at 115°C for 3 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (4). The hydroxyl group equivalent of this phenolic resin (4) was 72 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.2.

Next, 72 parts by mass of phenolic resin (4) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (4). The epoxy equivalent of this epoxy resin (4) was 158 g/equivalent.

(Synthesis Example 5: Production of Epoxy Resin (5))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 320 parts by mass of toluene, 220 parts by mass of resorcinol, and 4.4 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 260 parts by mass of 1,4-divinylbenzene was added dropwise over 3 hours, and the mixture was held at 115°C for 7 hours. 4.6 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (5). The hydroxyl group equivalent of this phenolic resin (5) was 131 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 1.0.

Next, 131 parts by mass of phenolic resin (5) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (5). The epoxy equivalent of this epoxy resin (5) was 219 g/equivalent.

(Synthesis Example 6: Production of Epoxy Resin (6))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 329 parts by mass of toluene, 220 parts by mass of resorcinol, and 4.4 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 273 parts by mass of 1,4-divinylbenzene was added dropwise over 3 hours, and the mixture was held at 115°C for 7 hours. 4.6 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (6). The hydroxyl group equivalent of this phenolic resin (6) was 135 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 1.05.

Next, 135 parts by mass of phenolic resin (6) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and then 1,000 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a crude reaction product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (6). The epoxy equivalent of this epoxy resin (6) was 223 g/equivalent.

(Synthesis Example 7: Production of epoxy resin (7))
283 parts by mass of toluene, 216 parts by mass of orthocresol, and 2.2 parts by mass of paratoluenesulfonic acid were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 115°C under a nitrogen atmosphere. 208 parts by mass of 1,4-divinylbenzene were added dropwise over 2 hours, and the mixture was held at 115°C for 5 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution were added, and the toluene was removed at 170°C to obtain a phenolic resin (7). The hydroxyl group equivalent of this phenolic resin (7) was 219 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of orthocresol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.8.

Next, 219 parts by mass of phenolic resin (7) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a reaction crude product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (7). The epoxy equivalent of this epoxy resin (7) was 300 g/equivalent.

(Synthesis Example 8: Production of epoxy resin (8))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 300 parts by mass of toluene, 320 parts by mass of 1,6-dihydroxynaphthalene, and 3.2 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 130 parts by mass of 1,4-divinylbenzene was added dropwise over 2 hours, and the mixture was held at 115°C for 5 hours. 3.4 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (8). The hydroxyl group equivalent of this phenolic resin (8) was 119 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of 1,6-dihydroxynaphthalene corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.5.

Next, 119 parts by mass of phenolic resin (8) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a reaction crude product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and then the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (8). The epoxy equivalent of this epoxy resin (8) was 206 g/equivalent.

(Synthesis Example 9: Production of epoxy resin (9))
285 parts by mass of toluene, 220 parts by mass of catechol, and 2.2 parts by mass of paratoluenesulfonic acid were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 115°C under a nitrogen atmosphere. 208 parts by mass of 1,4-divinylbenzene were added dropwise over 2 hours, and the mixture was held at 115°C for 5 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution were added, and the toluene was removed at 170°C to obtain a phenolic resin (9). The hydroxyl group equivalent of this phenolic resin (9) was 110 g/equivalent. The number of moles of 1,4-divinylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of catechol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.8.

Next, 110 parts by mass of phenolic resin (9) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a reaction crude product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (9). The epoxy equivalent of this epoxy resin (9) was 199 g/equivalent.

(Synthesis Example 10: Production of epoxy resin (10))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 409 parts by mass of toluene, 220 parts by mass of resorcinol, and 4.4 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 394 parts by mass of diallyl phthalate were added dropwise over 3 hours, and the mixture was held at 115°C for 8 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution were added, and the toluene was removed at 170°C to obtain a phenolic resin (10). The hydroxyl group equivalent of this phenolic resin (10) was 161 g/equivalent. The number of moles of diallyl phthalate corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.8.

Next, 161 parts by mass of phenolic resin (10) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and then 1,000 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a reaction crude product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (10). The epoxy equivalent of this epoxy resin (10) was 249 g/equivalent.

(Synthesis Example 11: Production of epoxy resin (11))
To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 315 parts by mass of toluene, 220 parts by mass of resorcinol, and 2.2 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 115°C under a nitrogen atmosphere. 253 parts by mass of 1,4-diisopropenylbenzene was added dropwise over 2 hours, and the mixture was held at 115°C for 5 hours. 2.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (11). The hydroxyl group equivalent of this phenolic resin (11) was 123 g/equivalent. The number of moles of 1,4-diisopropenylbenzene corresponding to the aromatic compound (a2) defined in the present invention relative to 1 mole of resorcinol corresponding to the compound (a1) having a phenolic hydroxyl group defined in the present invention was 0.8.

Next, 123 parts by mass of phenolic resin (11) was dissolved in 462.5 parts by mass of epichlorohydrin in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and then 1,000 parts by mass of 20% by mass aqueous sodium hydroxide was dropped at 80°C over 5 hours while stirring, and the reaction was continued for another hour. Next, the aqueous layer was discarded by a separation operation, and the excess epichlorohydrin present in the organic layer was recovered by distillation to obtain a reaction crude product. 250 parts by mass of methyl isobutyl ketone was added to the organic layer to dissolve the contents uniformly, and then the organic layer was washed with water. Next, water was removed from the organic layer by azeotropic distillation, and the precipitated insoluble matter was removed by filtration, and then the methyl isobutyl ketone was distilled off to obtain the desired epoxy resin (11). The epoxy equivalent of this epoxy resin (11) was 211 g/equivalent.

(Example 1: Preparation of acrylate resin (1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 58 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1), and then 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain acrylate resin (1). The nonvolatile content of this acrylate resin (1) was 80% by mass, and the epoxy equivalent of the resin content was 481 g/equivalent. The acid value was measured based on the neutralization titration method of JIS K 0070 (1992). The number of moles of acrylic acid per mole of epoxy groups in epoxy resin (1) was 0.5.

(Example 2: Preparation of acrylate resin (2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 53 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 18 parts by mass of acrylic acid and 0.6 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 9 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.6 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (2). The non-volatile content of this acrylate resin (2) was 80 mass%, and the epoxy equivalent of the resin was 297 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (1) was 0.25.

(Example 3: Preparation of acrylate resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 52 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 10.8 parts by mass of acrylic acid and 0.6 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 7 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.6 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (3). The non-volatile content of this acrylate resin (3) was 80 mass%, and the epoxy equivalent of the resin was 253 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (1) was 0.15.

(Example 4: Preparation of acrylate resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 62 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 54 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 15 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (4). The non-volatile content of this acrylate resin (4) was 80 mass%, and the epoxy equivalent of the resin was 1015 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (1) was 0.75.

(Example 5: Preparation of acrylate resin (5))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 64 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1), and then 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 61.2 parts by mass of acrylic acid and 0.8 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 100 ° C. for 17 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.8 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (5). The non-volatile content of this acrylate resin (5) was 80% by mass, and the epoxy equivalent of the resin was 1756 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (1) was 0.85.

(Example 6: Preparation of acrylate resin (6))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by mass of methyl isobutyl ketone and 178 parts by mass of epoxy resin (2), and then 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.6 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.6 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain an acrylate resin (6). The non-volatile content of this acrylate resin (6) was 80% by mass, and the epoxy equivalent of the resin was 447 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (2) was 0.5.

(Example 7: Preparation of acrylate resin (7))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 50 parts by mass of methyl isobutyl ketone and 164 parts by mass of epoxy resin (3), and then 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.6 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.6 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain acrylate resin (7). The non-volatile content of this acrylate resin (7) was 80% by mass, and the epoxy equivalent of the resin was 421 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (3) was 0.5.

(Example 8: Preparation of acrylate resin (8))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 49 parts by mass of methyl isobutyl ketone and 158 parts by mass of epoxy resin (4) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.6 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 12 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.6 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (8). The non-volatile content of this acrylate resin (8) was 80 mass%, and the epoxy equivalent of the resin was 401 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (4) was 0.5.

(Example 9: Preparation of acrylate resin (9))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 64 parts by mass of methyl isobutyl ketone and 219 parts by mass of epoxy resin (5) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.8 parts by mass of triphenylphosphine, and carrying out an esterification reaction at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.8 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain acrylate resin (9). The non-volatile content of this acrylate resin (9) was 80% by mass, and the epoxy equivalent of the resin was 533 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (5) was 0.5.

(Example 10: Preparation of acrylate resin (10))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 65 parts by mass of methyl isobutyl ketone and 223 parts by mass of epoxy resin (6), and then 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.8 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.8 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain an acrylate resin (10). The non-volatile content of this acrylate resin (10) was 80% by mass, and the epoxy equivalent of the resin was 539 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in the epoxy resin (6) was 0.5.

(Example 11: Preparation of acrylate resin (11))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 84 parts by mass of methyl isobutyl ketone and 300 parts by mass of epoxy resin (7) were charged, and 0.2 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 1.0 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 12 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 1.0 part by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (11). The non-volatile content of this acrylate resin (11) was 80 mass%, and the epoxy equivalent of the resin was 699 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (7) was 0.5.

(Example 12: Preparation of acrylate resin (12))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 61 parts by mass of methyl isobutyl ketone and 206 parts by mass of epoxy resin (8) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine, and carrying out an esterification reaction at 100°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain an acrylate resin (12). The non-volatile content of this acrylate resin (12) was 80% by mass, and the epoxy equivalent of the resin was 501 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in the epoxy resin (8) was 0.5.

(Example 13: Preparation of acrylate resin (13))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 59 parts by mass of methyl isobutyl ketone and 199 parts by mass of epoxy resin (9) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 12 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (13). The non-volatile content of this acrylate resin (13) was 80 mass%, and the epoxy equivalent of the resin was 493 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (9) was 0.5.

(Example 14: Preparation of acrylate resin (14))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 71 parts by mass of methyl isobutyl ketone and 249 parts by mass of epoxy resin (10) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.9 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100°C for 12 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.9 parts by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain acrylate resin (14). The non-volatile content of this acrylate resin (14) was 80% by mass, and the epoxy equivalent of the resin was 597 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (10) was 0.5.

(Example 15: Preparation of acrylate resin (15))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 62 parts by mass of methyl isobutyl ketone and 211 parts by mass of epoxy resin (11) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 36 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 12 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain acrylate resin (15). The non-volatile content of this acrylate resin (15) was 80 mass%, and the epoxy equivalent of the resin was 515 g / equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in epoxy resin (11) was 0.5.

(Example 16: Preparation of acrylate resin (16))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 114 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by addition of 36 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine, and an esterification reaction was carried out at 120°C for 8 hours while blowing in air. Next, 1.4 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain an acrylate resin (16). The non-volatile content of this acrylate resin (16) was 70% by mass, and the epoxy equivalent of the resin was 15520 g/equivalent. In addition, the number of moles of acrylic acid per mole of epoxy group in the epoxy resin (1) was 1.0.

(Example 17: Preparation of methacrylate resin (1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 60 parts by mass of methyl isobutyl ketone and 195 parts by mass of epoxy resin (1) were charged, and 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, followed by adding 43 parts by mass of methacrylic acid and 0.7 parts by mass of triphenylphosphine, and esterification reaction was carried out at 100 ° C. for 10 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.7 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain methacrylate resin (1). The nonvolatile content of this methacrylate resin (1) was 80 mass%, and the epoxy equivalent of the resin was 499 g / equivalent. In addition, the number of moles of methacrylic acid per mole of epoxy group in epoxy resin (1) was 0.5.

(Comparative Example 1: Preparation of Acrylate Resin (R1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 344 parts by mass of bisphenol A type epoxy resin (DIC Corporation "EPICLON EXA-850CRP", epoxy equivalent 172 g/equivalent), 0.21 parts by mass of dibutylhydroxytoluene and 0.21 parts by mass of methoquinone were added, and then 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100 ° C. for 10 hours while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.42 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an acrylate resin (R1). The epoxy equivalent of the resin content of this acrylate resin (R1) was 445 g/equivalent.

(Example 18: Preparation of curable resin composition (1))
100 parts by mass of the acrylate resin (1) having a non-volatile content of 80% by mass obtained in Example 1, 20 parts by mass of an acrylate monomer, 5 parts by mass of a photopolymerization initiator ("Omnirad 184D" manufactured by IGM Resins), and 1.6 parts by mass of 2-ethyl-4-methyl-imidazole were mixed to obtain a curable resin composition (1).

(Examples 19 to 34: Preparation of curable resin compositions (2) to (17))
Curable resin compositions (2) to (16) were obtained in the same manner as in Example 18, except that the acrylate resin (1) used in Example 18 was replaced with the acrylate resin (2) to (16) having a non-volatile content of 80% by mass obtained in Examples 2 to 17 and the methacrylate resin (1) in the amounts shown in Tables 1 and 2.

(Comparative Example 2: Preparation of Curable Resin Composition (R1))
100 parts by mass of the acrylate resin (R1) having a non-volatile content of 80% by mass obtained in Comparative Example 1, 20 parts by mass of an acrylate monomer, 5 parts by mass of a photopolymerization initiator ("Omnirad 184D" manufactured by IGM Resins), and 1.6 parts by mass of 2-ethyl-4-methyl-imidazole were mixed to obtain a curable resin composition (R1).

The following evaluations were carried out using the curable resin compositions (1) to (17) and (R1) obtained in the above examples and comparative examples.

[Method of measuring elongation]
The elongation was measured based on a tensile test.
<Preparation of Test Piece 1>
The curable resin compositions obtained in the Examples and Comparative Examples were applied onto copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, irradiated with ultraviolet light of 10 kJ/ ^m2 using a metal halide lamp, and then heated at 160° C. for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product).

<Tensile test>
The test piece 1 was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine "Autograph AG-IS" manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured, and evaluated according to the following criteria.

Measurement conditions: temperature 23°C, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm/min

[Method of measuring dielectric constant]
The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, after irradiating ultraviolet rays of 10 kJ/m ² using a metal halide lamp, the coating was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Then, the test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the dielectric constant of the test piece at 1 GHz was measured by a cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

[Method of measuring dielectric tangent]
The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, after irradiating ultraviolet rays of 10 kJ/m ² using a metal halide lamp, the coating was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Then, the test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by a cavity resonance method using a "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc.

The compositions and evaluation results of the curable resin compositions (1) to (17) prepared in Examples 18 to 34 and the curable resin composition (R1) prepared in Comparative Example 2 are shown in Tables 1 and 2.

The parts by mass of acrylate resin and methacrylate resin in Tables 1 and 2 are solids values.

In addition, "Acrylate Monomer" in Table 1 refers to EO-modified diacrylate of bisphenol A ("Miramaer M240" manufactured by Miwon Specialty Chemical Co., Ltd.).

"Photopolymerization initiator" in Table 1 refers to "Omnirad 184D" manufactured by IGM Resins.

Examples 18 to 34 shown in Tables 1 and 2 are examples of curable resin compositions using the acrylate resin of the present invention. It was confirmed that the acrylate resin of the present invention has excellent elongation and dielectric properties in the cured product.

On the other hand, Comparative Example 2 is an example of a curable resin composition using an acrylate resin made from an epoxy resin that does not use an aromatic compound having at least two ethylenically unsaturated bonds. It was confirmed that this curable resin composition also has insufficient elongation and dielectric properties.

Claims (7)

An epoxy resin (A),
An unsaturated monobasic acid (B);
A (meth)acrylate resin having as an essential raw material
The epoxy resin (A) is produced using, as essential raw materials, a compound (a1) having a phenolic hydroxyl group, an aromatic compound (a2) having at least two ethylenically unsaturated bonds, and an epihalohydrin (a3),
The aromatic compound (a2) is divinylbenzene and/or diisopropenylbenzene,
The (meth)acrylate resin is characterized in that the amount of the aromatic compound (a2) used is in the range of 0.25 to 1 mole per mole of the compound (a1) having a phenolic hydroxyl group . The (meth)acrylate resin according to claim 1, wherein the amount of the unsaturated monobasic acid (B) used is in the range of 0.2 to 0.8 moles of acid groups of the unsaturated monobasic acid (B) per mole of epoxy groups of the epoxy resin (A). 3. The (meth)acrylate resin according to claim 1, which has an epoxy group and a (meth)acryloyl group. A curable resin composition comprising the epoxy (meth)acrylate resin according to any one of claims 1 to 3 and a photopolymerization initiator. The curable resin composition according to claim 4 , further comprising a (meth)acrylate monomer. A cured product of the curable resin composition according to claim 4 or 5 . An article having a coating film comprising the cured product according to claim 6 .