Curable resin composition, cured product and related products

Abstract

To provide a curable resin composition which can form a cured product having excellent heat resistance and dielectric characteristics, a cured product of the curable resin composition, and an article having a coating film comprising the cured product.SOLUTION: There are used: a curable resin composition which contains a curable resin (A) having a structure represented by general formula (1) and having at least one polymerizable unsaturated group at a molecular terminal, and a photopolymerization initiator (B); a cured product of the curable resin composition; and an article having a coating film comprising the cured product. [In the formula (1), Ra and Rb are each independently a C1-12 alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group; X is a C1-50 hydrocarbon group; Y is the following general formula (1-1) or (1-2); and k is an integer of 0-3.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, a cured product of the curable resin composition, and an article having a coating film made of the cured product. [Background technology]

[0002] 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 thermosetting compositions that can be cured by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. In particular, for the coating agent applications, it is generally required that the coating agent be capable of imparting design features to the surfaces of various substrates, have excellent curability, 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 can form cured coating films that not only have curability but also have performance such as heat resistance at a level that can protect the coated object even under various temperature environments.

[0003] Known techniques for improving the heat resistance of cured coating films include curable compositions containing di(meth)acrylates represented by the following general formula (see, for example, Patent Document 1).

[0004] [ka] [In the above formula, R1 represents a hydrogen atom or a methyl group.]

[0005] However, the heat resistance of the curable composition in the cured coating film is insufficient, and the dielectric properties do not satisfy the increasingly high performance requirements of today.

[0006] Therefore, there is a need for a material that has excellent heat resistance and dielectric properties. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-314320 Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, a cured product of the curable resin composition, and an article having a coating film made of the cured product. [Means for solving the problem]

[0009] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a curable resin composition containing a specific curable resin and a photopolymerization initiator, and have completed the present invention.

[0010] That is, the present invention relates to a curable resin composition characterized by containing a curable resin (A) having a structure represented by the following general formula (1) and at least one polymerizable unsaturated group at a molecular terminal, and a photopolymerization initiator (B), as well as a cured product of the curable resin composition, an insulating material, and a resist member.

[0011] [ka]

[0012] [In formula (1), Ra and Rb each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms. X represents a hydrocarbon group having 1 to 50 carbon atoms, Y represents the following general formula (1-1) or (1-2), and k represents an integer of 0 to 3.]

[0013] [ka]

[0014] [ka]

[0015] [In formula (1-2), Z is an alicyclic group, an aromatic group, or a heterocyclic group.] [Effects of the Invention]

[0016] The curable resin composition of the present invention can form a cured product having excellent heat resistance and dielectric properties, and therefore can be used as a coating agent or adhesive. As a coating agent, the composition is particularly suitable for use as a solder resist. In the present invention, "excellent dielectric properties" refer to a low dielectric constant and a low dielectric loss tangent. DETAILED DESCRIPTION OF THE INVENTION

[0017] The curable resin composition of the present invention is characterized by containing a curable resin (A) having a structure represented by general formula (1) and at least one polymerizable unsaturated group at a molecular terminal, and a photopolymerization initiator (B).

[0018] The curable resin (A) has a structure represented by the following general formula (1) and has at least one polymerizable unsaturated group at the molecular end.

[0019] [ka]

[0020] [In formula (1), Ra and Rb each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms. X represents a hydrocarbon group having 1 to 50 carbon atoms, Y represents the following general formula (1-1) or (1-2), and k represents an integer of 0 to 3.]

[0021] [ka]

[0022] [ka]

[0023] [In formula (1-2), Z is an alicyclic group, an aromatic group, or a heterocyclic group.]

[0024] In the above formula (1), Ra and Rb are preferably each independently an alkyl group, an aryl group, or a cycloalkyl group having 1 to 4 carbon atoms, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0025] In the above formula (1), X may be any hydrocarbon group having 1 to 50 carbon atoms. However, structures represented by the following general formulas (1-3) to (1-6) are preferred, and the structure represented by the following general formula (1-3) is more preferred, as this gives a curable resin composition that can form a cured product having excellent heat resistance and dielectric properties.

[0026] [ka]

[0027] [In formula (1-3), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group.]

[0028] [ka]

[0029] [ka]

[0030] [In formula (1-5), R 1 and R 2are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group.]

[0031] [ka] [In formula (1-6), n is an integer of 0 to 2.]

[0032] In the above formula (1), Y is preferably the above formula (1-2) because a curable resin composition capable of forming a cured product excellent in heat resistance and dielectric properties can be obtained.

[0033] In the above formula (1-2), Z is preferably a structure represented by the following general formulas (1-2a) to (1-2e), since a curable resin composition capable of forming a cured product excellent in heat resistance and dielectric properties can be obtained.

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] Examples of the polymerizable unsaturated group include a (meth)acryloyloxy group, a vinylbenzyl ether group, an allyl ether group, etc. These polymerizable unsaturated groups can be used alone or in combination of two or more.

[0040] Furthermore, since the curable resin (A) can be a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, it is preferable that the formula (1) has a structure represented by the following general formula (1A):

[0041] [ka]

[0042] [In formula (1A), Ra and Rb each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and Rc each independently represents hydrogen or a methyl group. Y is represented by the above general formula (1-1) or (1-2)]

[0043] The curable resin (A) has a structure represented by the above formula (1) and is characterized by having at least one polymerizable unsaturated group at a molecular terminal, but may contain a plurality of structures represented by the above formula (1) as repeating units as long as the properties of the curable resin (A) are not impaired.

[0044] The weight average molecular weight (Mw) of the curable resin (A) is preferably in the range of 500 to 50,000, more preferably in the range of 1,000 to 10,000, and even more preferably in the range of 1,500 to 5,000, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0045] <Method for producing curable resin> The method for producing the curable resin (A) will be described below.

[0046] Examples of the production method include a method of reacting in an organic solvent, such as interfacial polymerization, and a method of reacting in a molten state, such as melt polymerization.

[0047] <Interfacial polymerization method> Examples of the interfacial polymerization method include a method in which a solution (organic phase) obtained by dissolving a dicarboxylic acid halide and a crosslinking group-introducing agent used to introduce a polymerizable unsaturated group (crosslinking group) as a terminal structure in a water-immiscible organic solvent is mixed with an alkaline aqueous solution (aqueous phase) containing a dihydric phenol, a polymerization catalyst, and an antioxidant, and a polymerization reaction is carried out while stirring at a temperature of 50°C or less for 1 to 8 hours; a method in which a solution (organic phase) obtained by dissolving a crosslinking group-introducing agent used to introduce a polymerizable unsaturated group (crosslinking group) as a terminal structure in a water-immiscible organic solvent is mixed with an alkaline aqueous solution (aqueous phase) containing a dihydric phenol, a polymerization catalyst, and an antioxidant, and a polymerization reaction is carried out while stirring at a temperature of 50°C or less for 1 to 8 hours.

[0048] The organic solvent used in the organic phase is preferably a solvent that is incompatible with water and dissolves polyarylate, such as chlorine-based solvents such as methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-, m-, and p-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, and xylene, and tetrahydrofuran.

[0049] Examples of the alkaline aqueous solution used in the aqueous phase include an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.

[0050] Examples of the antioxidant include 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, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 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, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,3-diphenyl-4-phenylenediamine), and methyl-p-benzoquinone.Amine compounds such as 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 products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-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-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of antioxidants include zinc compounds such as 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 distearyl 3,3'-thiodipropionate. These antioxidants can be used alone or in combination.

[0051] Commercially available antioxidants include, for example, "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.

[0052] Examples of the polymerization catalyst include quaternary ammonium salts such as tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide; and quaternary phosphonium salts such as tri-n-butylbenzylphosphonium halide, tetra-n-butylphosphonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide. Among these, tri-n-butylbenzylammonium halide, trimethylbenzylammonium halide, tetra-n-butylammonium halide, tri-n-butylbenzylphosphonium halide, and tetra-n-butylphosphonium halide are preferred because they can produce polymers with high molecular weights and low acid values.

[0053] The amount of the polymerization catalyst added is preferably 0.01 to 5.0 mol%, more preferably 0.1 to 1.0 mol%, based on the number of moles of dihydric phenol used in polymerization. If the amount of the polymerization catalyst added is less than 0.01 mol%, the effect of the polymerization catalyst cannot be obtained and the molecular weight of the polyarylate resin tends to be low, which is not preferable. On the other hand, if the amount exceeds 5.0 mol%, the hydrolysis reaction of the divalent aromatic carboxylic acid halide becomes rapid, which also tends to be low, which is not preferable.

[0054] Examples of the dihydric phenol include 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,6-dimethylphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5,6-trimethylphenyl)propane, 2,2-bis(4-hydroxy-2,3,6-trimethylphenyl)propane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,6-dimethylphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5,6-trimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, bis(4-hydroxy-3,5-dimethylphenyl)methane Examples of suitable dihydric phenols include bis(4-hydroxy-3,5-dimethylphenyl)butane, bis(4-hydroxy-3,5-dimethylphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethane, 1,3-bis(2-(4-hydroxy-3,5-dimethylphenyl)-2-propyl)benzene, 1,4-bis(2-(4-hydroxy-3,5-dimethylphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 2,2-bis(2-hydroxy-5-biphenylyl)propane, and 2,2-bis(4-hydroxy-3-cyclohexyl-6-methylphenyl)propane. These dihydric phenols can be used alone or in combination of two or more.

[0055] Examples of the dicarboxylic acid halide include terephthalic acid halide, isophthalic acid halide, orthophthalic acid halide, diphenic acid halide, biphenyl-4,4'-dicarboxylic acid halide, 1,4-naphthalenedicarboxylic acid halide, 2,3-naphthalenedicarboxylic acid halide, 2,6-naphthalenedicarboxylic acid halide, 2,7-naphthalenedicarboxylic acid halide, 1,8-naphthalenedicarboxylic acid halide, 1,5-naphthalenedicarboxylic acid halide, diphenyl ether-2,2'-dicarboxylic acid halide, diphenyl ether-2,3'-dicarboxylic acid halide, diphenyl ether-2,4'-dicarboxylic acid halide, diphenyl ether-3,3'-dicarboxylic acid halide, diphenyl ether-3,4'-dicarboxylic acid halide, diphenyl ether-4,4'-dicarboxylic acid halide, 1,4-cyclohexanedicarboxylic acid halide, and 1,3-cyclohexanedicarboxylic acid halide. These dicarboxylic acid halides can be used alone or in combination of two or more.

[0056] <Melt polymerization method> Examples of the melt polymerization method include a method in which a dihydric phenol as a raw material is acetylated, and then the acetylated dihydric phenol and a dicarboxylic acid are subjected to deacetylation polymerization, and a method in which a dihydric phenol and a carbonate ester are subjected to an ester exchange reaction.

[0057] In the acetylation reaction, an aromatic dicarboxylic acid component, a dihydric phenol component, and acetic anhydride are charged into a reaction vessel. The atmosphere is then purged with nitrogen, and the mixture is stirred under normal pressure or pressure in an inert atmosphere at a temperature of 100 to 240°C, preferably 120 to 180°C, for 5 minutes to 8 hours, preferably 30 minutes to 5 hours. The molar ratio of acetic anhydride to the hydroxyl groups of the dihydric phenol component is preferably in the range of 1 to 1.2, since this results in a curable resin composition capable of forming a cured product with excellent heat resistance and dielectric properties.

[0058] The deacetylation polymerization reaction is a reaction in which an acetylated dihydric phenol and a dicarboxylic acid are reacted and polycondensed. The reaction temperature in the deacetylation polymerization reaction is preferably 240°C or higher, more preferably 260°C or higher, and even more preferably 280°C or higher, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The degree of reduced pressure is preferably 500 Pa or lower, more preferably 260 Pa or lower, and even more preferably 130 Pa or lower, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The holding time is preferably 30 minutes or longer, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0059] In the acetylation reaction and the deacetylation polymerization reaction, a catalyst can be used as needed. Examples of the catalyst include organic titanate compounds such as tetrabutyl titanate; zinc acetate; alkali metal salts such as potassium acetate; alkaline earth metal salts such as magnesium acetate; antimony trioxide; organic tin compounds such as hydroxybutyltin oxide and tin octoate; and heterocyclic compounds such as N-methylimidazole. The amount of the catalyst added is preferably 1.0 mol % or less, more preferably 0.5 mol % or less, and even more preferably 0.2 mol % or less, based on the total monomer components of the resulting polyarylate resin.

[0060] The reaction temperature in the transesterification reaction is preferably in the range of 120 to 260°C, more preferably 160 to 200°C, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The reaction time is preferably 0.1 to 5 hours, more preferably 0.5 to 6 hours, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The pressure is preferably from atmospheric pressure to 1 Torr, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0061] Examples of catalysts for the transesterification reaction include zinc, tin, zirconium, and lead salts. These catalysts can be used alone or in combination of two or more. Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, and lead(IV) acetate. The amount of the catalyst used is preferably in the range of 0.000001 to 0.1 mol%, more preferably 0.00001 to 0.01 mol%, per mol of the total dihydric phenol.

[0062] As the dihydric phenol, the same dihydric phenols as those exemplified above can be used, and the dihydric phenols can be used alone or in combination of two or more kinds.

[0063] Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, diphenic acid, biphenyl-4,4'-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more.

[0064] Examples of the carbonate ester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. These carbonate esters can be used alone or in combination of two or more.

[0065] The curable resin (A) has at least one polymerizable unsaturated group as a terminal structure, and a crosslinking group-introducing agent can be used to introduce the polymerizable unsaturated group (crosslinking group). Examples of the crosslinking group-introducing agent include (meth)acrylic anhydride, (meth)acrylic acid chloride, chloromethylstyrene, chlorostyrene, allyl chloride, and allyl bromide. Among these, (meth)acrylic anhydride and (meth)acrylic acid chloride are preferred because they can produce a curable resin composition that can form a cured product with excellent heat resistance and dielectric properties.

[0066] Examples of the (meth)acrylic anhydride include acrylic anhydride and methacrylic anhydride. Examples of the (meth)acrylic acid chloride include methacrylic acid chloride and acrylic acid chloride. Examples of the chloromethylstyrene include p-chloromethylstyrene and m-chloromethylstyrene, examples of the chlorostyrene include p-chlorostyrene and m-chlorostyrene, examples of the allyl chloride include 3-chloro-1-propene, and examples of the allyl bromide include 3-bromo-1-propene. These can be used alone or in combination of two or more. Among these, methacrylic anhydride and methacrylic acid chloride are preferred because they can provide a curable resin composition that can form a cured product having excellent heat resistance and dielectric properties.

[0067] The content of the curable resin (A) in the curable resin composition of the present invention is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0068] Examples of the photopolymerization initiator (B) 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.

[0069] Commercially available products of the photopolymerization initiator (B) 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", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure Examples of suitable photopolymerization initiators (B) include "Quantacure 55" (manufactured by Stoffa Chemical Co.), "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ Co.), "DEAP" (manufactured by Upjohn Chemical Co.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop Co.), and "Runtecure 1104" (manufactured by Runtec Co.). These photopolymerization initiators (B) can be used alone or in combination of two or more.

[0070] The amount of the photopolymerization initiator (B) added is, for example, preferably in the range of 0.05 to 15 mass %, more preferably in the range of 0.1 to 10 mass %, of the total of the components other than the solvent of the curable resin composition.

[0071] The method for producing the curable resin composition of the present invention is not particularly limited, and any method may be used. For example, the curable resin composition may be produced by mixing the components including the curable resin (A) and the photopolymerization initiator (B). The mixing method is not particularly limited, and a paint shaker, disperser, roll mill, bead mill, ball mill, attritor, sand mill, bead mill, etc. may be used.

[0072] The curable resin composition of the present invention may contain other resin components in addition to the curable resin (A). Examples of the other resin components include a resin (C) having a polymerizable unsaturated group.

[0073] The resin (C) 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, ester resins having a polymerizable unsaturated group, etc. Examples of the polymerizable unsaturated group include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, etc.

[0074] 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, 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, a polybasic acid anhydride.

[0075] Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0076] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0077] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0078] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0079] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0080] Examples of the unsaturated monobasic acid 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 (2) can also be used.

[0081] [ka] [In formula (2), Q 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. P represents a hydrogen atom or a methyl group.]

[0082] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0083] The (poly)ester chain includes, for example, a (poly)ester chain represented by the following general formula (2-1).

[0084] [ka] [In formula (2-1), R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0085] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, 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.

[0086] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (2-2).

[0087] [ka] [In formula (2-2), R 2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0088] The molecular weight of the compound represented by the general formula (2) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0089] These unsaturated monobasic acids can be used alone or in combination of two or more.

[0090] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0091] Examples of the aliphatic polybasic acid anhydrides include acid 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, 1,2,3,4-butanetetracarboxylic acid, etc. Furthermore, 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.

[0092] 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 an aromatic ring in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include 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 anhydrides.

[0093] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0094] These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0095] Examples of the polyisocyanate compound 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 (3); 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.

[0096] [ka] [In formula (3), R 1 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.

[0097] The (meth)acrylate compound having a hydroxyl group is not particularly limited in terms of its specific structure as long as it has a hydroxyl group and a (meth)acryloyl group in its molecular structure, and a wide variety of compounds can be used. Examples of such acrylates 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, and ditrimethylolpropane tri(meth)acrylate. Also usable are (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 has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

[0098] 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, if necessary, and may also use a basic catalyst, if necessary.

[0099] 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 ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; and 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. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, as this improves reaction efficiency.

[0100] Examples of the basic catalyst include 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 amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. Examples of suitable ammonium salts include quaternary ammonium salts such as 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 octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. 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. 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.

[0101] 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.

[0102] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0103] 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 types.

[0104] 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 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 various polyol compounds; lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various polyol compounds; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The above-mentioned polyol compounds can be used alone or in combination of two or more.

[0105] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0106] 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, if necessary, and may also use a basic catalyst, if necessary.

[0107] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0108] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0109] Examples of the acrylic resin having a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing, as an essential component, 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, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product, if necessary.

[0110] The acrylic resin intermediate may be copolymerized with 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 compounds may be used alone or in combination of two or more.

[0111] 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 preferred from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred 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 preferred 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 preferred 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 preferred to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compounds (β) can be used alone or in combination of two or more kinds.

[0112] 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.

[0113] 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, if necessary, and may also use a basic catalyst, if necessary.

[0114] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0115] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0116] Examples of the amide-imide resin having a polymerizable unsaturated group include those 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.

[0117] The amide-imide resin may have either an acid group or an acid anhydride group, or 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 for the resin to have an acid anhydride group, and it is more preferable for the resin to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0118] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0119] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0120] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0121] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0122] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. 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 Examples of suitable polybasic acids include 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, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0123] 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 types.

[0124] 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.

[0125] 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, if necessary, and may also use a basic catalyst, if necessary.

[0126] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0127] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0128] 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 alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

[0129] The compound 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 (4-1) to (4-5).

[0130] [ka]

[0131] In the above structural formulas (4-1) to (4-5), R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. Furthermore, 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. For example, in the naphthalene ring of structural formula (4-2), the substituent may be on any ring; in structural formula (4-3), the substituent may be on any ring of the benzene ring present in one molecule; in structural formula (4-4), the substituent may be on any ring of the benzene ring present in one molecule; and in structural formula (4-5), the substituent may be on any ring of the benzene ring present in one molecule; and p and q indicate the number of substituents in one molecule.

[0132] The compound having a phenolic hydroxyl group may also be, for example, a reaction product obtained by using, as essential reaction raw materials, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (5-1) to (5-5): Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule.

[0133] 7 [ka]

[0134] [In formula (5-1), h is 0 or 1. In formulas (5-2) to (5-5), R 1 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 of 1 to 4. In formulas (5-2), (5-3), and (5-5), each W is independently any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (5-5), V 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 of 1 to 4.

[0135] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0136] 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 can provide 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.

[0137] 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 that can form a cured product having excellent heat resistance and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

[0138] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

[0139] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0140] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0141] 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, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0142] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0143] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0144] Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins, and heteropolyhydrochloric acids. Among these, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid are preferred.

[0145] 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 alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

[0146] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as compounds having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more types.

[0147] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties. The alkylene oxide may be used alone or in combination of two or more.

[0148] The alkylene carbonate may be the same as those exemplified above. 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 heat resistance and dielectric properties. The alkylene carbonate may be used alone or in combination of two or more.

[0149] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0150] As the polybasic acid anhydride, the same polybasic acid anhydrides as those exemplified above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0151] 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, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0152] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0153] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0154] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0155] Furthermore, various (meth)acrylate monomers can also be used as the resin (C) having a polymerizable unsaturated group.

[0156] Examples of the (meth)acrylate monomer 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; and 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; aromatic compounds such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate. Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propanediol, etc. Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic 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;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 above-mentioned 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 above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which 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 compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(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 aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds.

[0157] In addition to the above, the (meth)acrylate monomer may also be a (meth)acrylate monomer having a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

[0158] Examples of the phenol compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

[0159] Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. These cyclic carbonate compounds can be used alone or in combination of two or more.

[0160] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran, etc. These cyclic ether compounds can be used alone or in combination of two or more.

[0161] As the unsaturated monocarboxylic acid, the same unsaturated monobasic acids as those exemplified above can be used.

[0162] The amount of the resin (C) having a polymerizable unsaturated group used is preferably such that the mass ratio of the solid contents of the curable resin (A) to the resin (C) having a polymerizable unsaturated group [(A) / (C)] is 5 / 95 to 95 / 5, and more preferably 10 / 90 to 90 / 10, since a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained.

[0163] Furthermore, the curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as needed.

[0164] 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.

[0165] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0166] Examples of the polybasic acid 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, and bicyclo[2.2.1]heptacarboxylic acid. Examples of suitable polybasic acids include 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 suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0167] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0168] Examples of the amine compound 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.

[0169] Examples of the amide compounds include dicyandiamide, polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more.

[0170] Examples of the azo compounds include azobisisobutyronitrile.

[0171] Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, alkyl peroxycarbonate, etc. These organic peroxides can be used alone or in combination of two or more.

[0172] Examples of the polyol compound 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 above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. Examples of suitable polyols include polyester polyols obtained by co-condensation of the above polyol monomers 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 of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and 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.

[0173] As the epoxy resin, the same epoxy resins as those exemplified above can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0174] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0175] 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, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0176] As the polymerization inhibitor, the same ones as those exemplified above as antioxidants can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds.

[0177] As the antioxidant, the same antioxidants as those exemplified above can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0178] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0179] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0180] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0181] Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0182] 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, and zinc sulfide.

[0183] Examples of the organic pigment 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.

[0184] 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 obtained by reacting them 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-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0185] 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 ultraviolet curing reaction.

[0186] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0187] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0188] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0189] Furthermore, because 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., or adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCD and OELD as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. Among these, it is particularly suitable for use as a solder resist.

[0190] The article of the present invention has a coating film made of the cured product, and examples of such articles include plastic molded products such as mobile phones, home appliances, automotive interior / exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices. [Example]

[0191] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0192] In the examples of the present application, the weight average molecular weight of the curable resin was measured by gel permeation chromatography (GPC) under the following conditions.

[0193] Measurement equipment: Tosoh Corporation "HLC-8220 GPC" Column: Tosoh Corporation guard column "HXL-L" +Tosoh Corporation "TSK-GEL G2000HXL" +Tosoh Corporation "TSK-GEL G2000HXL" +Tosoh Corporation's "TSK-GEL G3000HXL" +Tosoh Corporation's "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation "GPC-8020 Model II Version 4.10" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the "GPC-8020 Model II Version 4.10," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: 1.0% by mass of tetrahydrofuran solution (equivalent to resin solids) filtered through a microfilter (50 μl)

[0194] (Synthesis Example 1: Production of Curable Resin (A1)) A reaction vessel equipped with a stirrer was charged with 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.0 parts by mass of sodium hydroxide, 0.25 parts by mass of tri-n-butylbenzylammonium chloride, and 2,000 parts by mass of pure water, and dissolved to prepare an aqueous phase.An organic phase was prepared by dissolving 30.5 parts by mass of terephthalic acid dichloride, 30.5 parts by mass of isophthalic acid dichloride, and 20.9 parts by mass of methacrylic acid chloride in 1,500 parts by mass of methylene chloride.

[0195] Next, the aqueous phase was stirred in advance, and the organic phase was added to the aqueous phase under strong stirring and allowed to react at 20°C for 5 hours. After this, the stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed 10 times with pure water. After this, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator, and the polymer obtained by the reaction was dried. The obtained polymer was dried under reduced pressure to obtain a curable resin (A1) having the following structure, a terminal methacryloyloxy group, and a weight average molecular weight of 3100.

[0196] [ka]

[0197] (Synthesis Example 2: Production of Curable Resin (A2)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 102.5 parts by mass of bis(4-hydroxy-3,5-dimethylphenyl)methane, to obtain a curable resin (A2) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 2900.

[0198] [ka]

[0199] (Synthesis Example 3: Production of Curable Resin (A3)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 141.0 parts by mass of 2,2-bis(2-hydroxy-5-biphenylyl)propane, to obtain a curable resin (A3) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 3,200.

[0200] [ka]

[0201] (Synthesis Example 4: Production of Curable Resin (A4)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 157.0 parts by mass of 2,2-bis(4-hydroxy-3-cyclohexyl-6-methylphenyl)propane, to obtain a curable resin (A4) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 3,200.

[0202] [ka]

[0203] (Synthesis Example 5: Production of Curable Resin (A5)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5,6-trimethylphenyl)propane, to obtain a curable resin (A5) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 3,100.

[0204] [ka]

[0205] (Synthesis Example 6: Production of Curable Resin (A6)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 129.8 parts by mass of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, to obtain a curable resin (A6) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 3,100.

[0206] [ka]

[0207] (Synthesis Example 7: Production of Curable Resin (A7)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 1 above was changed to 161.0 parts by mass of 1,4-bis(2-(4-hydroxy-3,5-dimethylphenyl)-2-propyl)benzene, to obtain a curable resin (A7) having the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 3,500.

[0208] [ka]

[0209] (Synthesis Example 8: Production of Curable Resin (A8)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the terephthalic acid dichloride and isophthalic acid dichloride in Synthesis Example 1 were changed to 62.7 parts by mass of 1,4-cyclohexanedicarboxylic acid dichloride, to obtain a curable resin (A8) having the following structure, a methacryloyloxy group at its terminal, and a weight-average molecular weight of 3,100.

[0210] [ka]

[0211] (Synthesis Example 9: Production of Curable Resin (A9)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the terephthalic acid dichloride and isophthalic acid dichloride in Synthesis Example 1 were changed to 88.5 parts by mass of diphenyl ether-4,4'-dicarboxylic acid dichloride, to obtain a curable resin (A9) having the following structure, a methacryloyloxy group at its terminal, and a weight-average molecular weight of 3,500.

[0212] [ka]

[0213] (Synthesis Example 10: Production of Curable Resin (A10)) A reaction vessel equipped with a stirrer, distillation column, and pressure reducing device was charged with 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.2 parts by mass of diphenyl carbonate, and 0.01 parts by mass of tetramethylammonium hydroxide. The mixture was then purged with nitrogen and dissolved at 140°C. After stirring for 30 minutes, the internal temperature was raised to 180°C and the reaction was carried out for 30 minutes at an internal pressure of 100 mmHg, and the resulting phenol was distilled off. The internal temperature was then raised to 200°C while gradually reducing the pressure, and the reaction was carried out for 30 minutes at 50 mmHg while distilling off the phenol. The temperature was then gradually increased to 220°C and 1 mmHg, the pressure was reduced, and the reaction was carried out for 30 minutes at the same temperature and pressure. The resulting solid was washed with methanol and then dried under reduced pressure to obtain an intermediate compound.

[0214] Next, 20 g of toluene and 22 parts by weight of the intermediate compound were mixed in a 200 mL flask equipped with a thermometer, condenser, and stirrer and heated to approximately 85°C. 0.19 parts by weight of dimethylaminopyridine was added. Once all solids appeared to have dissolved, 30.6 parts by weight of methacrylic anhydride was slowly added. The resulting solution was maintained at 85°C for 3 hours with continuous mixing. The solution was then cooled to room temperature and added dropwise to methanol in a 1 L beaker that was being vigorously stirred with a magnetic stirrer. The resulting precipitate was filtered under reduced pressure and dried to obtain a curable resin (A10) with the following structure, a terminal methacryloyloxy group, and a weight-average molecular weight of 2700.

[0215] [ka]

[0216] (Synthesis Example 11: Production of Curable Resin (A11)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the methacrylic acid chloride in Synthesis Example 1 was changed to 30.5 parts by mass of chloromethylstyrene, to obtain a curable resin (A11) having the following structure, a terminal vinylbenzyl ether group, and a weight-average molecular weight of 3,100.

[0217] [ka]

[0218] (Synthesis Example 12: Production of Curable Resin (A12)) Synthesis was carried out in the same manner as in Synthesis Example 1 above, except that the methacrylic acid chloride in Synthesis Example 1 was changed to 15.3 parts by mass of allyl chloride, to obtain a curable resin (A12) having the following structure, an allyl ether group at its terminal, and a weight-average molecular weight of 3,100.

[0219] [ka]

[0220] (Synthesis Example 13: Production of curable resin (A13)) A reaction vessel equipped with a stirrer was charged with 91.3 parts by mass of 2,2-bis(4-hydroxyphenyl)propane, 64.0 parts by mass of sodium hydroxide, 0.25 parts by mass of tri-n-butylbenzylammonium chloride, and 2,000 parts by mass of pure water, and dissolved to prepare an aqueous phase.An organic phase was prepared by dissolving 30.5 parts by mass of terephthalic acid dichloride and 30.5 parts by mass of isophthalic acid dichloride in 1,500 parts by mass of methylene chloride.

[0221] Next, the aqueous phase was stirred in advance, and the organic phase was added to the aqueous phase under strong stirring, and the reaction was allowed to proceed at 20°C for 5 hours. After this, the stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed with a 10% aqueous acetic acid solution, followed by 10 times with pure water. After this, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator, and the polymer obtained by the reaction was dried. The obtained polymer was dried under reduced pressure to obtain a curable resin (A13) having the following repeating unit and a weight average molecular weight of 3000, which had a terminal methacryloyloxy group:

[0222] [ka]

[0223] (Synthesis Example 14: Production of Resin (C1) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 188 parts by mass of bisphenol A type epoxy resin (EPICLON 850-S manufactured by DIC Corporation, epoxy equivalent weight 188 g / equivalent), and 0.26 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.13 parts by mass of methoquinone as a thermal polymerization inhibitor were added. Thereafter, 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing in air, thereby obtaining a resin (C1) having a polymerizable unsaturated group.

[0224] (Synthesis Example 15: Production of Resin (C2) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (DIC Corporation's "EPICLON 850CRP," epoxy equivalent 173 g / equivalent). 0.21 parts by weight of dibutylhydroxytoluene as an antioxidant and 0.21 parts by weight of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by weight of acrylic acid and 0.21 parts by weight of triphenylphosphine were added, and the reaction was carried out at 100 ° C for 10 hours while blowing air. After confirming that the acid value was 1 mg KOH / g or less, 0.21 parts by weight of oxalic acid was added and the mixture was stirred at 70 ° C for 3 hours to obtain a resin (C2) having polymerizable unsaturated groups. The epoxy equivalent of this resin (C2) having polymerizable unsaturated groups was 450 g / equivalent.

[0225] (Example 1: Preparation of curable resin composition (1)) The curable resin (A1) obtained in Synthesis Example 1 and a photopolymerization initiator (B1) ("Omnirad 907" manufactured by IGM; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) were mixed to obtain a curable resin composition, and then methyl ethyl ketone and 2-ethyl-4-methylimidazole were added in the parts by mass shown in Table 1 to obtain a curable resin composition (1).

[0226] (Examples 2 to 14: Preparation of curable resin compositions (2) to (14)) Using the compositions and blending ratios shown in Tables 1 and 2, curable resin compositions (2) to (14) were obtained in the same manner as in Example 1.

[0227] (Comparative Example 1: Preparation of curable resin composition (R1)) The curable resin (A13) obtained in Synthesis Example 13 and a photopolymerization initiator (B1) ("Omnirad 907" manufactured by IGM; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) were mixed to obtain a curable resin composition, and then methyl ethyl ketone and 2-ethyl-4-methylimidazole were added in the parts by mass shown in Table 2 to obtain a curable resin composition (R1).

[0228] The curable resin compositions (1) to (14) and (R1) obtained in the above examples and comparative examples were evaluated as follows.

[0229] [Heat resistance evaluation method] The curable resin compositions obtained in each of the Examples and Comparative Examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied curable resin compositions to a copper foil to a thickness of 50 μm. 2 After irradiating the film with ultraviolet light, the film was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 35 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). Note that a higher glass transition temperature indicates better heat resistance.

[0230] [Method for measuring dielectric constant] The curable resin composition obtained in each of the Examples and Comparative Examples 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, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored for 24 hours in a room at 23°C and 50% humidity to prepare a test piece. The dielectric constant of the test piece at 1 GHz was measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. by the cavity resonance method.

[0231] [Method for measuring dielectric loss tangent] The curable resin composition obtained in each of the Examples and Comparative Examples 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, a metal halide lamp was used to apply 10 kJ / m 2After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0232] Tables 1 and 2 show the compositions and evaluation results of the curable resin compositions (1) to (14) and (R1) obtained in the above examples and comparative examples.

[0233] [Table 1]

[0234] [Table 2]

[0235] In Tables 1 and 2, the parts by mass of the curable resin and the resin having a polymerizable unsaturated group are solid content values.

[0236] "Acrylate monomer" in Table 2 refers to bisphenol A EO-modified diacrylate ("Miramer M-240" manufactured by MIWON Co., Ltd.).

[0237] Examples 1 to 14 shown in Tables 1 and 2 are examples of curable resin compositions using the curable resin composition of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance and dielectric properties.

[0238] On the other hand, Comparative Example 1 is an example of a curable resin composition that does not contain the curable resin represented by general formula (1). It was confirmed that the cured product of this curable resin composition had a high dielectric constant and dielectric loss tangent, and its dielectric properties were significantly insufficient.

Claims

1. The composition contains a curable resin (A) having a structure represented by the following general formula (1A) and at least one polymerizable unsaturated group at a molecular terminal, a photopolymerization initiator (B), and a resin (C) having a polymerizable unsaturated group: The curable resin composition is characterized in that the mass ratio of the solid content of the curable resin (A) to the solid content of the resin having a polymerizable unsaturated group (C), [(A) / (C)], is in the range of 5 / 95 to 95 / 5. 【Chemistry 1】 [In formula (1A), Ra and Rb each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and Rc each independently represents a hydrogen atom or a methyl group. Y is represented by the following general formula (1-1) or (1-2)] 【Chemistry 2】 【Transformation 3】 [In formula (1-2), Z is an alicyclic group, an aromatic group, or a heterocyclic group.]

2. The polymerizable unsaturated group is a (meth)acryloyloxy group, a vinylbenzyl ether group, The curable resin composition according to claim 1, wherein the alkyl group is an alkyl ether group or an allyl ether group.

3. A curable resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the curable resin (A) is in the range of 500 to 50,000.

4. A curable resin composition according to any one of claims 1 to 3, wherein the resin (C) having a polymerizable unsaturated group is an epoxy resin having a polymerizable unsaturated group, a urethane resin having a polymerizable unsaturated group, an acrylic resin having a polymerizable unsaturated group, an amide-imide resin having a polymerizable unsaturated group, an acrylamide resin having a polymerizable unsaturated group, an ester resin having a polymerizable unsaturated group, or a (meth)acrylate monomer.

5. A cured product of the curable resin composition according to any one of claims 1 to 4.

6. An article having a coating film made of the cured product according to claim 5.

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