JP7615865B2 - Epoxy (meth)acrylate resin, curable resin composition, cured product and article - Google Patents

Description

The present invention relates to an epoxy (meth)acrylate resin, a curable resin composition, a cured product, and an article.

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, and the like. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent be capable of imparting design to the surface of various substrates, have excellent curing properties, and be capable of forming a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding materials that not only have the heat resistance of the obtained cured product but also have excellent dielectric properties.

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 is known as a conventional active energy ray curable composition (see, for example, Patent Document 1). However, this composition does not satisfy the increasingly high heat resistance required, and its dielectric properties are also insufficient to meet current market demands.

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

Japanese Patent Application Publication No. 8-259663

The problem that the present invention aims to solve is to provide an epoxy (meth)acrylate resin, a curable resin composition, a cured product, and an article that can form a cured product having excellent heat resistance and dielectric properties.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using an epoxy (meth)acrylate resin in which a specific epoxy resin and an unsaturated monobasic acid are essential reaction raw materials, and thus completed the present invention.

That is, the present invention relates to an epoxy (meth)acrylate resin, a curable resin composition, a cured product, and an article, characterized in that the essential reaction raw materials are an epoxy resin (A) represented by the following general formula (1) and an unsaturated monobasic acid (B).

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

The epoxy (meth)acrylate resin of the present invention can form a cured product having excellent heat resistance and dielectric properties, so a curable resin composition containing the epoxy (meth)acrylate resin and a photopolymerization initiator can be suitably used as a coating agent or adhesive. In the present invention, "excellent dielectric properties" refers to a low dielectric constant and a low dielectric tangent.

The epoxy (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 reaction 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) is represented by the following general formula (1):

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and cyclohexyl groups.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, and an alkoxynaphthyl group.

The epoxy equivalent of the epoxy resin (A) is preferably in the range of 160 to 300 g/equivalent, more preferably in the range of 170 to 270 g/equivalent, and even more preferably in the range of 170 to 250 g/equivalent, since this results in an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties.

The melt viscosity of the epoxy resin (A) at 150°C is preferably in the range of 0.1 to 2 dPa·s, and more preferably in the range of 0.1 to 1 dPa·s, since this produces an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties.

The method for producing the epoxy resin (A) can be, for example, a method for epoxidizing a polyfunctional phenolic resin.

The epoxidation method is not particularly limited and any known technique can be used as appropriate. For example, a method of epoxidizing a polyfunctional phenolic resin by reacting it with epihalohydrin can be mentioned.

The polyfunctional phenolic resin may be, for example, one represented by the following general formula (2):

[In formula (2), R ¹ 's are each independently a hydrogen atom or an alkyl group, R ² 's are each independently a hydrogen atom or an alkyl group, R ³ 's are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.]

In addition, in the formula (2), the bonding position between the naphthalene ring and the methylene group, which may have a substituent, is arbitrary, and indicates that the bonding may be on a ring having a hydroxyl group or on a ring not having a hydroxyl group, and when l is 2 or more, the structures may be the same or different.

The alkyl group can be the same as the alkyl group described above.

The aryl group can be the same as the aryl group described above.

The method for producing the polyfunctional phenolic resin is not particularly limited, and any method may be used. For example, a method of reacting a naphthol compound, a catechol compound, and an aldehyde compound may be used.

Examples of the naphthol compound include α-naphthol, β-naphthol, and various dihydroxynaphthalenes, which may have a substituent. These naphthol compounds may be used alone or in combination of two or more. Among these, it is preferable to use unsubstituted β-naphthol, since it is possible to obtain an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties.

Examples of the catechol compounds include catechol, methylcatechol, n-butylcatechol, sec-butylcatechol, t-butylcatechol, 4-octylcatechol, and 3,5-di-t-butylcatechol. These catechol compounds can be used alone or in combination of two or more.

Examples of the aldehyde compounds include formaldehyde, trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, and hexamethylenetetramine. These aldehyde compounds can be used alone or in combination of two or more. Among these, it is preferable to use formaldehyde, since it can produce an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties. The formaldehyde may be used as formalin in the form of an aqueous solution, or as paraformaldehyde in the form of a solid.

The ratio of naphthol compound to catechol compound used is preferably in the molar ratio naphthol compound/catechol compound = 7/3 to 3/7, since this produces an epoxy (meth)acrylate resin capable of forming a cured product with excellent heat resistance and dielectric properties.

From the viewpoint of controlling the molecular weight distribution, the ratio of the raw materials used is preferably in the range of 0.1 to 1.1 moles of the aldehyde compound per 1 mole of the naphthol compound and catechol compound combined.

The reaction between the naphthol compound, the catechol compound, and the aldehyde compound can be carried out under the same conditions as in a normal novolak reaction. If necessary, the reaction may be carried out in an organic solvent, and if necessary, a reaction catalyst may be used.

Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; 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; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of suitable organic solvents include alcohol solvents such as propylene glycol monomethyl ether and propyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; 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. The amount of the organic solvent used is preferably in the range of 10 to 1,000 parts by mass per 100 parts by mass of the total amount of the naphthol compound and the catechol compound used.

Examples of the reaction catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as oxalic acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These reaction catalysts can be used alone or in combination of two or more. The amount of the reaction catalyst used is preferably in the range of 1 to 20 parts by mass per 100 parts by mass of the total amount of the naphthol compound and the catechol compound used.

The reaction temperature in the reaction between the naphthol compound, the catechol compound, and the aldehyde compound is preferably in the range of 60 to 180°C, and the reaction is preferably carried out while distilling off the water produced in the reaction. The reaction time is preferably 1 to 16 hours, and more preferably 2 to 12 hours.

The above reaction produces a polyfunctional phenolic resin represented by the general formula (2), which may contain other by-products. The by-products may be removed to extract and use only the compound represented by the general formula (2), but it may also be used as a precursor to the epoxy resin (A) while still containing the by-products.

In addition, the polyfunctional phenolic resin may be used in combination with other compounds having a phenolic hydroxyl group as long as the effects of the present invention are not impaired.

As the other compound having a phenolic hydroxyl group, for example, a compound having at least one phenolic hydroxyl group in the molecule can be used.

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

In the above general 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 general formula is arbitrary, and for example, in the naphthalene ring of general formula (1-2), it may be substituted on any ring, in general formula (1-3), it may be substituted on any ring of the benzene ring present in one molecule, and in general 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 other compound having a phenolic hydroxyl group, for example, a reaction product in which a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general 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 other compounds having a phenolic hydroxyl group can be used alone or in combination of two or more.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and β-methylepibromohydrin. These epihalohydrins can be used alone or in combination of two or more. Among these, epichlorohydrin is preferred.

The reaction between the polyfunctional phenolic resin and the epihalohydrin can be carried out, for example, by adding 1 to 10 moles of the epihalohydrin per mole of hydroxyl groups contained in the polyfunctional phenolic resin, and then reacting for 0.5 to 10 hours at a temperature of 20 to 120°C while adding 0.9 to 2.0 moles of a basic catalyst per mole of hydroxyl groups in the raw material all at once or gradually. The basic catalyst may be in the form of a solid or an aqueous solution. 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 the water may be removed by liquid separation while the epihalohydrin is continuously returned to the reaction mixture.

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.

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, tri Examples of the quaternary ammonium salts include octylmethylammonium acetate; phosphines 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. These basic catalysts can be used alone or in combination of two or more.

The reaction between the polyfunctional phenolic resin and the epihalohydrin may be carried out in an organic solvent as necessary. The organic solvent may be the same as the organic solvent exemplified above. The organic solvent may be used alone or in combination of two or more. The reaction product obtained by the reaction may be washed with water, and then the unreacted epihalohydrin and the organic solvent used may be distilled off by heating under reduced pressure. Furthermore, in order to obtain an epoxy resin with a low hydrolyzable halogen content, the reaction product obtained, i.e., the epoxy resin, may 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 may be added to further react. In this case, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present in order to improve the reaction rate. When a phase transfer catalyst is used, the amount of the catalyst used is preferably in the range of 0.1% by mass to 3.0% by mass relative to the epoxy resin used. After the reaction is complete, the salts formed are removed by filtration and washing with water, and the solvents such as toluene and methyl isobutyl ketone are distilled off under reduced pressure with heating to obtain a high-purity epoxy resin.

In addition, in the reaction between the polyfunctional phenolic resin and the epihalohydrin, a side reaction may occur, causing cyclization between adjacent hydroxyl groups in the catechol structure, or between a hydroxyl group on a benzene ring and a hydroxyl group on a naphthalene ring. Such by-products may be removed, or may be used as they are as epoxy resin (A).

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. Acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (3) can also be used.

[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 general formula (X-1):

[In formula (X-1), 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.

The (poly)carbonate chain may be, for example, a (poly)carbonate chain represented by the following general formula (X-2):

[In formula (X-2), R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

The molecular weight of the compound represented by the general formula (3) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400.

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), since this produces an epoxy (meth)acrylate resin capable of forming a cured product with excellent heat resistance and dielectric properties.

The epoxy (meth)acrylate resin of the present invention can also use compounds other than the epoxy resin (A) and the unsaturated monobasic acid (B) as raw materials, if necessary.

Examples of the other compounds include unsaturated monobasic acid anhydrides.

Examples of the unsaturated monobasic acid anhydride include acrylic acid anhydride and methacrylic acid anhydride. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more kinds.

The total mass ratio of the epoxy resin (A) and the unsaturated monobasic acid (B) in the raw material (solid content) of the epoxy (meth)acrylate resin of the present invention is preferably 60 mass% or more, since this gives an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties.

The method for producing the epoxy (meth)acrylate resin of the present invention is not particularly limited, and any method may be used. 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 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 amount of the basic catalyst used is preferably in the range of 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.8 parts by mass, per 100 parts by mass of the epoxy resin (A) and the unsaturated monobasic acid (B) in total, since an epoxy (meth)acrylate resin capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

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 epoxy (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 above-mentioned epoxy (meth)acrylate resin of the present invention (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 general formula (4); and isocyanurate modified products, biuret modified products, and allophanate modified products of these. These polyisocyanate compounds can be used alone or in combination of two or more kinds.

［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、又は一般式（４）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 general formula (4) 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 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 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 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.

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.

The compound having a phenolic hydroxyl group may be the same as the compound (a1) having a phenolic hydroxyl group described above, and the compound having a phenolic hydroxyl group may 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 heat resistance 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 is possible to obtain a curable resin composition capable of forming a cured product having excellent heat resistance 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 as the unsaturated monobasic acid, 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 heat resistance 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 heat resistance 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 as the unsaturated monobasic acid, 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 Examples of the (meth)acrylate compounds having an isocyanate group include 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.

The curable resin composition of the present invention may also contain various additives, such as curing accelerators, ultraviolet absorbers, polymerization inhibitors, antioxidants, organic solvents, inorganic fillers, polymer particles, pigments, defoamers, viscosity adjusters, leveling agents, flame retardants, and storage stabilizers, as necessary.

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.

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 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.

In addition, since the cured product of the present invention has excellent heat resistance and dielectric properties, it can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, etc., and adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin display applications such as LCD and OELD as thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. Among these, it can be particularly suitably used for solder resist applications.

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: Synthesis of phenolic resin (a-1))
216.2 parts by mass of β-naphthol, 412.9 parts by mass of catechol, and 4.1 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. 140.4 parts by mass of 37% by mass formalin was added dropwise over 3 hours while maintaining the temperature. The reaction was further carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off while blowing in water vapor under reduced pressure at 150 ° C., thereby obtaining the desired phenolic resin (a-1). The phenolic hydroxyl group equivalent was 92 g / equivalent, the softening point was 94 ° C., and the melt viscosity at 150 ° C. was 5.6 dPa · s.

(Synthesis Example 2: Synthesis of phenolic resin (a-2))
216.2 parts by mass of β-naphthol, 330.3 parts by mass of catechol, and 6.6 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. 140.4 parts by mass of 37% by mass formalin was added dropwise over 3 hours while maintaining the temperature. The reaction was further carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off at 150 ° C. under reduced pressure while blowing in water vapor, thereby obtaining the desired phenolic resin (a-2). The phenolic hydroxyl group equivalent was 93 g / equivalent, the softening point was 101 ° C., and the melt viscosity at 150 ° C. was 8.8 dPa · s.

(Synthesis Example 3: Synthesis of phenolic resin (a-3))
216.2 parts by mass of β-naphthol, 495.5 parts by mass of catechol, and 9.9 parts by mass of distilled water were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and the temperature was raised to 150 ° C. while dissolving. While maintaining the temperature, 140.4 parts by mass of 37% by mass formalin was dropped over 3 hours. Furthermore, the reaction was carried out at 150 ° C. for 6 hours while the distillate water was expelled from the system. After the reaction, the unreacted catechol was distilled off while blowing in water vapor under reduced pressure at 150 ° C., thereby obtaining the desired phenolic resin (a-3). The phenolic hydroxyl group equivalent was 93 g / equivalent, the softening point was 91 ° C., and the melt viscosity at 150 ° C. was 4.5 dPa · s.

(Synthesis Example 4: Synthesis of epoxy resin (A-1))
A flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 230.0 parts by mass of phenolic resin (a-1) and 925.0 parts by mass of epichlorohydrin, and the temperature was raised to 50 ° C. while stirring and dissolving. Next, 2.30 parts by mass of benzyltrimethylammonium chloride was charged and reacted for 24 hours at 50 ° C. Furthermore, 224.5 parts by mass of 49% by mass aqueous sodium hydroxide solution was dropped over 3 hours, and the reaction was further carried out at 50 ° C. for 1 hour. After the reaction was completed, 185.0 parts by mass of n-butanol was added, stirring was stopped, the water layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 629.0 parts by mass of methyl isobutyl ketone and 105.0 parts by mass of n-butanol were added to the crude epoxy resin obtained and dissolved. Further, 47.0 parts by mass of a 10% by mass aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80°C for 2 hours, after which washing with 185.0 parts by mass of water was repeated until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin (A-1) was 181 g/equivalent, and the melt viscosity at 150°C was 0.5 dPa·s.

(Synthesis Example 5: Synthesis of epoxy resin (A-2))
The same operation as in Example 3 was carried out except that 230.0 parts by mass of the phenolic resin (a-1) was changed to 232.5 parts by mass of the phenolic resin (a-2), to obtain an epoxy resin (A-2). The epoxy equivalent of the obtained epoxy resin (A-2) was 192 g/equivalent, and the melt viscosity at 150° C. was 0.9 dPa·s.

(Synthesis Example 6: Synthesis of epoxy resin (A-3))
The same operation as in Example 3 was carried out except that 230.0 parts by mass of the phenolic resin (a-1) was changed to 232.5 parts by mass of the phenolic resin (a-3), to obtain an epoxy resin (A-3). The epoxy equivalent of the obtained epoxy resin (A-3) was 181 g/equivalent, and the melt viscosity at 150°C was 0.4 dPa·s.

(Synthesis Example 7: Synthesis of epoxy resin (A-4))
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 122.5 parts by mass of β-naphthol, 141.2 parts by mass of t-butylcatechol (DIC Corporation "DIC-TBC"), and 38.3 parts by mass of a 20% by mass aqueous solution of sodium hydroxide were charged and heated to 100 ° C. while dissolving. While maintaining the temperature, 71.0 parts by mass of 37% by mass formalin was dropped over 2 hours. Then, the mixture was reacted at 100 ° C. for 6 hours and cooled to room temperature. After neutralization with 26.4 parts by mass of sodium dihydrogen phosphate, 380 parts by mass of methyl isobutyl ketone was added and dissolved, washed with water, and methyl isobutyl ketone was distilled off under reduced pressure. Next, 1174.8 parts by mass of epichlorohydrin was charged, and the temperature was raised to 50 ° C. while stirring and dissolving. Next, 9.47 parts by mass of benzyltrimethylammonium chloride was charged, and the mixture was reacted for 24 hours while maintaining the temperature at 50 ° C. Further, 238.2 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was dropped over 3 hours, and further reacted at 50 ° C. for 1 hour. After the reaction was completed, 117.4 parts by mass of n-butanol was added, stirring was stopped, the water layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. The crude epoxy resin thus obtained was dissolved by adding 708.9 parts by mass of methyl isobutyl ketone and 105.0 parts by mass of n-butanol. Further, 33.8 parts by mass of a 10% by mass aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80 ° C. for 2 hours, after which the mixture was repeatedly washed with 209.0 parts by mass of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin (A-4). The epoxy equivalent of the obtained epoxy resin (A-4) was 237 g/equivalent, and the melt viscosity at 150° C. was 0.2 dPa·s.

(Example 1: Production of epoxy acrylate resin (1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-1), and after adding 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 36 parts by mass of acrylic acid and 0.1 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C. for 20 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (1). The non-volatile content of this epoxy acrylate resin (1) was 80 mass%, and the epoxy equivalent of the solid content was 538 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of epoxy resin (A-1) was 0.5 moles.

(Example 2: Production of epoxy acrylate resin (2))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 57 parts by mass of methyl isobutyl ketone and 192 parts by mass of epoxy resin (A-2), and then 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 0.1 parts by mass of triphenylphosphine, and the reaction was carried out at 100 ° C. for 20 hours while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (2). The non-volatile content of this epoxy acrylate resin (2) was 80 mass%, and the epoxy equivalent of the solid content was 551 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of epoxy resin (A-2) was 0.5 moles.

(Example 3: Production of epoxy acrylate resin (3))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 54 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-3), and then 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 0.1 parts by mass of triphenylphosphine, and the reaction was carried out at 100°C for 20 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (3). The nonvolatile content of this epoxy acrylate resin (3) was 80% by mass, and the epoxy equivalent of the solid content was 531 g/equivalent. In addition, the number of moles of acid groups of acrylic acid relative to 1 mole of epoxy groups of epoxy resin (A-3) was 0.5 moles.

(Example 4: Production of epoxy acrylate resin (4))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 68 parts by mass of methyl isobutyl ketone and 237 parts by mass of epoxy resin (A-4), and then 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 0.1 parts by mass of triphenylphosphine, and the reaction was carried out at 100 ° C. for 20 hours while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (4). The non-volatile content of this epoxy acrylate resin (4) was 80 mass%, and the epoxy equivalent of the solid content was 636 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of epoxy resin (A-4) was 0.5 moles.

(Example 5: Production of epoxy acrylate resin (5))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 49 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-1), and after adding 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 14.4 parts by mass of acrylic acid and 0.1 parts by mass of triphenylphosphine were added, and the reaction was carried out for 12 hours at 100 ° C. while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (5). The nonvolatile content of this epoxy acrylate resin (5) was 80 mass%, and the epoxy equivalent of the solid content was 297 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of epoxy resin (A-1) was 0.2 moles.

(Example 6: Production of epoxy acrylate resin (6))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 102 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-1), and after adding 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 57.6 parts by mass of acrylic acid and 0.7 parts by mass of triphenylphosphine were added, and the 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 the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (6). The nonvolatile content of this epoxy acrylate resin (6) was 70 mass%, and the epoxy equivalent of the solid content was 1530 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of epoxy resin (A-1) was 0.8 moles.

(Example 7: Production of epoxy acrylate resin (7))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 108 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-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 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine, and the reaction was carried out at 110°C for 12 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH/g or less, 1.3 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin 71). The nonvolatile content of this epoxy acrylate resin (7) was 70% by mass, and the epoxy equivalent of the solid content was 20340 g/equivalent. In addition, the number of moles of acid groups of acrylic acid relative to 1 mole of epoxy groups of epoxy resin (A-1) was 1 mole.

(Example 8: Production of epoxy methacrylate resin (1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 56 parts by mass of methyl isobutyl ketone and 181 parts by mass of epoxy resin (A-1), and after adding 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone, 43 parts by mass of methacrylic acid and 0.2 parts by mass of triphenylphosphine were added, and the reaction was carried out at 100 ° C. for 20 hours while blowing air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.2 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy methacrylate resin (1). The nonvolatile content of this epoxy methacrylate resin (1) was 80 mass%, and the epoxy equivalent of the solid content was 501 g / equivalent. In addition, the number of moles of acid groups of methacrylic acid per mole of epoxy groups of epoxy resin (A-1) was 0.5 moles.

(Comparative Example 1: Production of epoxy acrylate resin (R1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 208 parts by mass of t-butylcatechol type epoxy resin (DIC Corporation "EPICLON HP-820", epoxy equivalent: 208), 0.1 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone were added, and then 36 parts by mass of acrylic acid and 0.1 parts by mass of triphenylphosphine were added, and the reaction was carried out for 18 hours at 100 ° C. while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (R1). The nonvolatile content of this epoxy acrylate resin (R1) was 100 mass%, and the epoxy equivalent of the solid content was 502 g / equivalent. In addition, the number of moles of acid groups of acrylic acid relative to 1 mole of epoxy groups of the t-butylcatechol type epoxy resin was 0.5 moles.

(Comparative Example 2: Production of epoxy acrylate resin (R2))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 80 parts by mass of methyl isobutyl ketone and 204 parts by mass of a naphthalene-type epoxy resin (DIC Corporation's "EPICLON HP-4770", epoxy equivalent: 204), 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 0.1 parts by mass of triphenylphosphine, and the reaction was carried out at 100 ° C. for 23 hours while blowing in air. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.1 parts by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours to obtain the desired epoxy acrylate resin (R2). The nonvolatile content of this epoxy acrylate resin (R2) was 75% by mass, and the epoxy equivalent of the solid content was 509 g / equivalent. In addition, the number of moles of acid groups of acrylic acid per mole of epoxy groups of the naphthalene-type epoxy resin was 0.5 moles.

(Example 9: Preparation of curable resin composition (1))
100 parts by mass of the epoxy acrylate resin (1) having a nonvolatile content of 80% by mass obtained in Example 1 (80 parts by mass as solid content), 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-methylimidazole were mixed to obtain a curable resin composition (1).

(Examples 10 to 16: Preparation of curable resin compositions (2) to (8))
Curable resin compositions (2) to (8) were obtained in the same manner as in Example 9, except that the epoxy acrylate resin (1) used in Example 9 was replaced with the epoxy acrylate resins (2) to (7) and the epoxy methacrylate resin (1) obtained in Examples 2 to 8 in the amounts shown in Table 1.

(Comparative Example 3: Preparation of Curable Resin Composition (R1))
80 parts by mass of the acrylate resin (R1) having a non-volatile content of 100% 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-methylimidazole were mixed to obtain a curable resin composition (R1).

The following evaluations were carried out using the curable resin compositions (1) to (8), (R1) and (R2) obtained in the above examples and comparative examples.

[Method for evaluating heat resistance]
The curable resin composition obtained in each Example and Comparative Example was applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. Next, after irradiating with ultraviolet light of 10 kJ / m ² using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm x 35 mm was cut out from the cured product, and the temperature at which the elastic modulus change was maximum was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometrics Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C. / min). Note that a higher glass transition temperature indicates better heat resistance.

[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 (8) prepared in Examples 9 to 16 and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 3 and 4 are shown in Table 1.

The parts by mass of epoxy acrylate resin and epoxy methacrylate resin in Table 1 are solid content 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 9 to 16 shown in Table 1 are examples of curable resin compositions using the epoxy (meth)acrylate resin of the present invention. It was confirmed that the cured products of these curable resin compositions have excellent heat resistance and dielectric properties.

On the other hand, Comparative Examples 3 and 4 are examples of curable resin compositions that do not use the epoxy resin represented by general formula (1) as a raw material for the epoxy (meth)acrylate resin. The cured product of the curable resin composition obtained in Comparative Example 3 had extremely insufficient heat resistance, and the cured product of the curable resin composition obtained in Comparative Example 4 had both a high dielectric constant and a high dielectric loss tangent, and it was confirmed that the dielectric properties were extremely insufficient.

Claims (8)

An epoxy resin (A) represented by the following general formula (1);
An unsaturated monobasic acid (B);
An epoxy (meth)acrylate resin characterized by using as an essential reaction raw material.

[In formula (1), G is a glycidyl group, R1 ^'s are each independently a hydrogen atom or an alkyl group, ^R2 's are each independently a hydrogen atom or an alkyl group, R3 ^'s are each independently a hydrogen atom, an alkyl group, or an aryl group, n is an integer of 0 to 3, m is an integer of 0 to 6, l is an integer of 1 to 4, and n+l is 4.] The epoxy (meth)acrylate resin according to claim 1, wherein ^R2 and ^R3 in the general formula (1) are hydrogen atoms. The epoxy (meth)acrylate resin according to claim 1 or 2, wherein the number of moles of acid groups in the unsaturated monobasic acid (B) is in the range of 0.2 to 0.8 per mole of epoxy groups in the epoxy resin (A). The epoxy (meth)acrylate resin according to any one of claims 1 to 3, wherein the epoxy (meth)acrylate resin 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 4 and a photopolymerization initiator. The curable resin composition according to claim 5, further comprising a (meth)acrylate monomer. A cured product of the curable resin composition according to claim 5 or 6. An article having a coating film made of the cured product according to claim 7.