Resin composition containing a curable polymer compound

Abstract

The present invention provides a resin composition that can be molded into a film-like shape, and is such that a cured product thereof has high thermostability and adhesiveness and a low dielectric constant and dielectric loss tangent.　This resin composition includes: a polymer compound represented by formula (1) (in the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, and m and n represent the average number of repeating units and are each independently in the range between 1 and 2,000 inclusive); a compound that can radically polymerize with the polymer compound; and a radical initiator. The compound that can radically polymerize with the polymer compound is at least one selected from the group consisting of (A) phenylmaleimide compounds, (B) acenaphthylene compounds, (C) modified polyphenylene ether resins having an unsaturated double bond at an end, and (D) allyl isocyanurate compounds.

Description

[Technical Field]

[0001] The present invention relates to a composition containing a curable polymer compound having a specific structure, which can be easily formed into a film by casting a solution onto a substrate, can be cured by heat or light, and the cured product has excellent dielectric properties, adhesiveness, and heat resistance. [Background technology]

[0002] Phenoxy resin is a polymeric compound with a very high molecular weight obtained by polymerizing a difunctional epoxy resin and a difunctional phenolic compound. By adding this phenoxy resin, it is possible to turn general epoxy resin compositions and radically polymerizable compositions into films, and it is therefore used in a wide range of fields as an important component of film adhesives, particularly in the electrical and electronic fields where it is used for interlayer insulation layers in printed circuit boards and resin-coated copper foils. Although cured products of resin compositions containing added phenoxy resin have excellent adhesive properties and film-forming ability, they have low heat resistance and high dielectric constants and dielectric dissipation factors (typically, at a frequency of 1 GHz, the dielectric constant is about 3.5 and the dielectric dissipation factor is about 0.03), making them unsuitable for use in electronic devices, which have seen the recent increase in signal response speed. Polymeric fluorine compounds such as polytetrafluoroethane (PTFE) (Patent Document 1) and liquid crystal polymers (Patent Document 2) are generally known as resins with excellent dielectric properties, but these resins have extremely low compatibility with other resins and insufficient adhesion. Patent Document 3 describes a curable polymer compound obtained by esterifying a monomer having one or more ethylenically unsaturated groups and one carboxy group with an aliphatic hydroxyl group in a random copolymer of 70% by weight or less of a monomer having one ethylenically unsaturated group and 30% by weight or more of a (meth)acrylate having one or more aliphatic hydroxyl groups. However, when the present inventors conducted further tests, they found that the cured product of the curable polymer compound described in this document had a dielectric loss tangent of about 0.005 at 10 GHz, which does not fully satisfy the low dielectric properties required for current high-frequency circuit board applications. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-001274 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-060449 [Patent Document 3] Japanese Patent Application Publication No. 10-017812 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above points, and aims to provide a composition that has sufficient flexibility to be formed into a film, has high adhesion to low-roughness copper foil, has a low dielectric constant and dielectric dissipation factor, and a cured product with a high glass transition temperature. [Means for solving the problem]

[0005] As a result of intensive investigations, the present inventors have found that the above-mentioned problems can be solved by a composition comprising a polymer compound having a specific structure, a compound having a specific structure capable of radically polymerizing with the polymer compound, and a radical polymerization initiator, and have completed the present invention. That is, the present invention is (1) The following formula (1)

[0006] [ka]

[0007] (wherein R1 and R2 each independently represent a hydrogen atom or a methyl group; m and n each independently represent the average number of repeating units and are in the range of 1 to 2,000), a compound capable of radical polymerization with the polymer compound, and a radical initiator, wherein the compound capable of radical polymerization with the polymer compound is at least one selected from the group consisting of (A) a phenylmaleimide compound, (B) an acenaphthylene compound, (C) a modified polyphenylene ether resin having an unsaturated double bond at its terminal, and (D) an allyl isocyanurate compound; (2) The resin composition according to the above item (1), wherein the compound capable of radical polymerization with the polymer compound is a phenylmaleimide compound having one maleimide group in one molecule or a compound having one acenaphthylene structure in one molecule. (3) A film-like adhesive comprising the resin composition according to the preceding paragraph (1) or (2), and (4) A cured product of the resin composition described in the preceding item (1) or (2), or the film-like adhesive described in the preceding item (3). Regarding. [Effects of the Invention]

[0008] The resin composition of the present invention can be cured by applying heat or light energy, and can provide a cured product having excellent dielectric properties, adhesiveness, and heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described. The polymer compound represented by formula (1), which is an essential component of the resin composition of the present invention, is a dehydrochlorination condensation product of hydroxyl groups in a random copolymer of hydroxyphenyl (meth)acrylate and styrene with (meth)acrylic acid chloride groups, or a dehydration condensation product of hydroxyl groups in the copolymer with (meth)acrylic acid.

[0010] First, a random copolymer of hydroxyphenyl (meth)acrylate and styrene (hereinafter also simply referred to as "copolymer"), which is an intermediate raw material for the polymer compound represented by formula (1), will be described. Specific examples of hydroxyphenyl (meth)acrylate, a raw material for the copolymer, include 4-hydroxyphenyl methacrylate, 2-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, and 3-hydroxyphenyl acrylate, with 4-hydroxyphenyl methacrylate being preferred. In this specification, the term "(meth)acrylate" means both "acrylate and methacrylate."

[0011] The following formula (2) is the structural formula of a random copolymer of hydroxyphenyl (meth)acrylate and styrene, and R1, m, and n in formula (2) have the same meanings as R1, m, and n in formula (1). That is, the chemical polymer represented by formula (1) (polymer compound having a structure represented by formula (1)) is a polymer compound whose intermediate is a copolymer represented by formula (2):

[0012] [ka]

[0013] The method for copolymerizing hydroxyphenyl (meth)acrylate with styrene is not particularly limited as long as it is a known method, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Solvents that can be used in solution polymerization include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, N,N-dimethylformamide, and γ-butyrolactone. Emulsion polymerization and suspension polymerization usually use water and a surfactant, and the copolymerization reaction is carried out in a state where the raw material components are emulsified or suspended in water.

[0014] The copolymerization reaction may be any of radical polymerization, cationic polymerization, and anionic polymerization. In the case of radical polymerization, it is preferable to use a radical polymerization initiator. Specific examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. The amount of radical polymerization initiator blended is usually 0.001 to 5 parts by mass per 100 parts by mass of the total amount of raw material components of the copolymer. The polymerization temperature is usually 50 to 250°C, preferably 60 to 200°C, and the polymerization time is usually 0.5 to 30 hours, preferably 1 to 20 hours. The radical polymerization reaction is preferably carried out in a nitrogen gas atmosphere to prevent polymerization inhibition by oxygen in the air.

[0015] In the case of cationic polymerization, a cationic polymerization initiator can be used, and specific examples of the cationic polymerization initiator include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as CF3COOH and CCl3COOH, and super acids such as CF3SO3H and HClO4. In the case of anionic polymerization, an anionic polymerization initiator can be used, and specific examples of the anionic polymerization initiator include butyllithium, Na-naphthalene complex, alkali metal, alkyllithium compound, sodium amide, Grignard reagent, and lithium alkoxide. The amount of the cationic or anionic polymerization initiator is usually 0.01 to 5 parts by mass per 100 parts by mass of the raw materials for the copolymer. The polymerization temperature is usually 40 to 150°C, preferably 50 to 120°C, and the polymerization time is usually 0.5 to 20 hours, preferably 1 to 15 hours. However, there is a concern that the ionic initiators used in cationic polymerization and anionic polymerization may remain in the copolymer after the polymerization reaction and adversely affect the dielectric properties and insulating properties. Therefore, it is preferable to synthesize the copolymer that serves as the intermediate raw material for the polymer compound represented by formula (1) by radical polymerization.

[0016] The number average molecular weight of the copolymer serving as the intermediate raw material for the polymer compound represented by formula (1) is usually 3,000 to 300,000, preferably 5,000 to 200,000. In order to obtain a copolymer having a number average molecular weight within the above range, it is preferable to adjust the amount of initiator used when synthesizing the copolymer to an appropriate amount.The amount of initiator required to obtain a copolymer having a number average molecular weight within the above range depends on the type of (meth)acrylate having a phenolic hydroxyl group and the amount of (meth)acrylate having a hydroxyl group and styrene used in the copolymerization reaction, so it cannot be generally stated, but it is generally known that reducing the amount of initiator will result in a copolymer with a large molecular weight, and the amount of initiator to be added should be selected so that a copolymer with a desired molecular weight can be obtained within the above range.

[0017] The ratio of hydroxyphenyl (meth)acrylate to styrene used in synthesizing the copolymer serving as the intermediate raw material for the polymer compound represented by formula (1) is not particularly limited, but the amount (mass) of styrene used is usually 4 to 99.7 times, preferably 4.5 to 99.5 times, the mass of hydroxyphenyl (meth)acrylate. By using the raw materials for the copolymer in this range, the cured product of the resin composition of the present invention exhibits excellent dielectric properties (low dielectric constant and low dielectric loss tangent).

[0018] The polymer compound represented by formula (1) can be obtained by a dehydrochlorination reaction between the phenolic hydroxyl group of the copolymer (this hydroxyl group is the hydroxyl group originally possessed by the raw material hydroxyphenyl (meth)acrylate) and the chloride group of (meth)acrylic acid chloride, or by a dehydration condensation reaction between the phenolic hydroxyl group of the copolymer and (meth)acrylic acid.

[0019] The ratio of the copolymer and (meth)acrylic acid chloride or (meth)acrylic acid used when synthesizing the polymer compound represented by formula (1) is not particularly limited, but if there is an excess or an insufficient amount of (meth)acrylic acid chloride or (meth)acrylic acid relative to the hydroxyl groups in the copolymer, the unreacted (meth)acrylic acid chloride or (meth)acrylic acid remaining in the polymer compound represented by formula (1) and the hydroxyl groups remaining without reacting with (meth)acrylic acid chloride or methacrylic acid may adversely affect the properties of the cured product, so it is preferable to use an equivalent amount of (meth)acrylic acid chloride or (meth)acrylic acid to the hydroxyl groups in the copolymer.

[0020] The reaction between the copolymer and (meth)acrylic acid chloride can be carried out by adding (meth)acrylic acid chloride to a solution of the copolymer in an organic solvent under stirring. The organic solvent that can be used here is not particularly limited as long as it can dissolve the copolymer and (meth)acrylic acid chloride. When the copolymer serving as an intermediate raw material is synthesized in a solvent, the copolymer solution after the polymerization reaction can be used as is. The concentration of the copolymer solution to be reacted with (meth)acrylic acid chloride is usually 10 to 90% by mass, preferably 20 to 80% by mass. The reaction temperature is usually 30 to 120°C, preferably 40 to 110°C, and the reaction time is usually 0.5 to 4 hours, preferably 1 to 3 hours.

[0021] Since the reaction between the copolymer and (meth)acrylic acid chloride is a dehydrochlorination reaction, it is preferable to add a tertiary amine such as triethylamine or pyridine to the reaction solution in advance to trap the generated hydrochloric acid and further promote the reaction. The amount of tertiary amine used is preferably equimolar to 4 times the number of moles of (meth)acrylic acid chloride, more preferably equimolar to 3 times the number of moles. The hydrochloric acid generated during the reaction precipitates as the hydrochloride salt of the amine, and can be removed by filtration after the reaction. Furthermore, excess tertiary amine can be distilled out of the system after filtration under heating and reduced pressure.

[0022] The reaction between the copolymer and (meth)acrylic acid may be a conventionally known esterification reaction, and examples of methods for carrying out the reaction include heating and stirring the copolymer and (meth)acrylic acid in the presence of a catalyst. Because the reaction between the copolymer and (meth)acrylic acid is a dehydration reaction, it is preferable to carry out the reaction while azeotropically distilling off water from the reaction system. For this reason, it is preferable to carry out the reaction using a solvent that is completely immiscible with water, such as toluene, xylene, ethyl acetate, butyl acetate, and methyl isobutyl ketone. The amount of solvent used is preferably an amount that results in a concentration of the raw material components of the polymer compound represented by formula (1) of 20 to 80% by mass. Examples of catalysts used in the esterification reaction include acidic catalysts such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid, and the amount used is preferably 0.1 to 5 mass % based on the total mass of the raw materials for the polymer compound represented by formula (1) used in the reaction, the solvent, etc. The reaction temperature is usually 50 to 150°C, preferably 60 to 140°C, and the reaction time is usually 0.5 to 4 hours, preferably 1 to 3 hours.

[0023] In addition, in order to prevent polymerization reactions between (meth)acryloyl groups in the polymer compound represented by formula (1) and improve the storage stability of the polymer compound represented by formula (1), it is preferable to add a small amount of a polymerization inhibitor to the polymer compound solution after completion of the synthesis reaction. Specific examples of polymerization inhibitors include hydroquinone, paramethoxyphenol, methylhydroquinone, di-t-butylhydroxytoluene, t-butylhydroquinone, 2-t-butyl-1,4-benzoquinone, 1,4-benzoquinone, 1,1-diphenyl-2-picrylhydrazyl free radical, 6-t-butyl-2,4-xylenol, 4-t-butylpyrocatechol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, and phenothiazine.

[0024] The number-average molecular weight of the polymer compound represented by formula (1) thus obtained is preferably in the range of 11,000 to 300,000, more preferably 15,000 to 200,000. If the molecular weight is lower than this range, the adhesion to low-roughness copper foil will be reduced, and if it is higher, the viscosity will be high, which may make coating or the like difficult. The molecular weight in this specification means a value calculated in terms of polystyrene based on the results of GPC measurement.

[0025] The resin composition of the present invention contains, as a compound capable of radical polymerization with the polymer compound represented by formula (1), at least one compound selected from the group consisting of (A) a phenylmaleimide compound, (B) an acenaphthylene compound, (C) a modified polyphenylene ether resin having an unsaturated double bond at a terminal, and (D) an allyl isocyanurate compound.

[0026] (A) Phenylmaleimide compound (hereinafter simply referred to as "component (A)") The component (A) that can be contained in the resin composition of the present invention is added for the purpose of copolymerizing with the unsaturated double bond group that the polymer compound represented by formula (1) has at the side chain end. The number of maleimide groups in the compound is not particularly limited, but a phenylmaleimide compound having one maleimide group per molecule is preferred.

[0027] Examples of component (A) include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(3-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, and N-(4-t-butylphenyl)maleimide, with N-phenylmaleimide being preferred.

[0028] The content of component (A) in the resin composition of the present invention is usually 3 to 50 parts by mass, and preferably 5 to 40 parts by mass, per 100 parts by mass of the polymer compound represented by formula (1). By setting the content ratio of the polymer compound represented by formula (1) to component (A) within the above range, the cured product of the resin composition of the present invention will exhibit various excellent properties.

[0029] (B) Acenaphthylene compound (hereinafter simply referred to as "component (B)") The component (B) that can be contained in the resin composition of the present invention is added for the purpose of copolymerizing with the unsaturated double bond group that the polymer compound represented by formula (1) has at the side chain terminal, and the number of acenaphthylene structures in the compound is not particularly limited, but an acenaphthylene compound having one acenaphthylene structure in one molecule is preferred.

[0030] Examples of the component (B) include acenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 3,8-dimethylacenaphthylene, and 3,7-dimethylacenaphthylene, with acenaphthylene being preferred.

[0031] The content of component (B) in the resin composition of the present invention is usually 3 to 50 parts by mass, and preferably 5 to 40 parts by mass, per 100 parts by mass of the polymer compound represented by formula (1). By setting the content ratio of the polymer compound represented by formula (1) to component (B) within the above range, the cured product of the resin composition of the present invention will exhibit various excellent properties.

[0032] (C) Modified polyphenylene ether resin having an unsaturated double bond at the terminal (hereinafter simply referred to as "component (C)") The component (C) that can be contained in the resin composition of the present invention is preferably a modified polyphenylene ether resin having methacryloyl groups, acryloyl groups, or vinyl groups at both molecular terminals and a number-average molecular weight of 1,000 to 10,000. Specific examples include a compound represented by the following formula (3) (product name: SA9000, manufactured by SABIC Japan, LLC) having methacryloyl groups at both terminals and a number-average molecular weight of about 1,700, and a compound represented by the following formula (4) (product name: OPE-2St 1200 or OPE-2St 2200, manufactured by Mitsubishi Gas Chemical Company, Inc.) having vinyl groups at both terminals and a number-average molecular weight of about 1,200 or 2,200.

[0033] [ka]

[0034] [ka]

[0035] The content of the component (C) in the resin composition of the present invention is usually 3 to 50 parts by mass, and preferably 5 to 40 parts by mass, per 100 parts by mass of the polymer compound represented by formula (1).

[0036] (D) Allyl isocyanurate compound (hereinafter simply referred to as "component (D)") The component (D) that can be contained in the resin composition of the present invention is preferably an allyl isocyanurate compound having an isocyanurate structure and two or more allyl groups in one molecule, such as triallyl isocyanurate, 1,3-diallyl-5-methoxycarbonyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3-diallyl-5-(cyclohexen-4-yl)methoxycarbonyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. An example of an allyl isocyanurate compound having two allyl groups is L-DAIC manufactured by Shikoku Chemical Industry Co., Ltd. Monoallyl isocyanurate compounds having a functional group other than an allyl group that is capable of reacting with the polymer compound represented by formula (1) are also included in the category of component (D) contained in the composition of the present invention.

[0037] The content of component (D) in the resin composition of the present invention is usually 3 to 50 parts by mass, and preferably 5 to 40 parts by mass, per 100 parts by mass of the polymer compound represented by formula (1). By setting the content of component (D) relative to the polymer compound represented by formula (1) within the above range, the cured product of the resin composition of the present invention will exhibit various excellent properties.

[0038] The resin composition of the present invention contains a radical initiator. As the radical initiator, either a thermal radical initiator or a photoradical initiator can be used. Preferred thermal radical initiators include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilyl peroxide.

[0039] Examples of preferred photoradical initiators include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides, and xanthones.

[0040] The content of the radical initiator in the resin composition of the present invention is usually 0.1 to 10 parts by mass, preferably 0.1 to 8 parts by mass, relative to 100 parts by mass in total of the polymer compound represented by formula (1), the compound capable of radical polymerization with the polymer compound represented by formula (1), and resin components such as the optional radical-reactive monomer described below.

[0041] The resin composition of the present invention may contain a radical reactive monomer. By using a radical reactive monomer in combination, the reactivity of the resin composition of the present invention and the heat resistance of the cured product can be improved. The radical reactive monomer is preferably one having two or more functional groups, and specific examples thereof include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-Nonanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene oxide adduct methacrylate of bisphenol A, trimethylolpropane trimethacrylate, tricyclodecane dimethanol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, pentaerythritol Erythritol triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide, Np-chlorophenyl-maleimide Np-Methoxyphenyl-maleimide, Np-Methylphenyl-maleimide, Np-Nitrophenyl-maleimide, Np-Phenoxyphenyl-maleimide, Np-Phenylaminophenyl-maleimide, Np-Phenoxycarbonylphenyl-maleimide, 1-Maleimido-4-acetoxysuccinimide-benzene, 4-Maleimido-4'-acetoxysuccinimide-diphenylmethane, 4-Maleimido-4'-acetoxysuccinimide-diphenyl ether, 4-Maleimido-4'-acetamide -diphenyl ether, 2-maleimide-6-acetamido-pyridine, 4-maleimide-4'-acetamido-diphenylmethane, and Np-phenylcarbonylphenyl-maleimide N-ethylmaleimide, N-2,6-xylylmaleimide, N-cyclohexylmaleimide, N-2,3-xylylmaleimide, xylylmaleimide, 2,6-xylenemaleimide, and 4,4'-bismaleimidediphenylmethane are examples of such maleimide compounds, but those having a maleimide group as a functional group (maleimide compounds) are preferred. These radical reactive monomers may be used alone or in combination of two or more.

[0042] The resin composition of the present invention may contain an organic solvent. Specific examples of the organic solvent include aromatic solvents such as toluene and xylene, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone, lactones such as γ-butyrolactone and γ-valerolactone, amide solvents such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N,N-dimethylimidazolidinone, and sulfones such as tetramethylene sulfone. The content of the organic solvent in the resin composition of the present invention is usually 90% by mass or less, preferably 30 to 80% by mass, of the resin composition.

[0043] The resin composition of the present invention may contain a polymerization inhibitor in order to improve storage stability. The polymerization inhibitor that can be used in combination is not particularly limited as long as it is a commonly known polymerization inhibitor, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil, and trimethylquinone, aromatic diols, and di-t-butylhydroxytoluene.

[0044] The resin composition of the present invention can be blended with fillers and additives in amounts that do not impair the inherent performance, in order to impart desired performance depending on the application. The fillers may be fibrous or powdery, and examples of such fillers include silica, carbon black, alumina, talc, mica, glass beads, and glass hollow spheres.

[0045] The resin composition of the present invention can also contain flame-retardant compounds, additives, and the like. These compounds are not particularly limited as long as they are commonly used. Examples of flame-retardant compounds include bromine compounds such as 4,4-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicon-based compounds. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, and gloss agents. These additives can be used in combination as desired.

[0046] The resin composition of the present invention can be applied to or impregnated into various substrates. For example, when a thermal radical initiator is used, it can be applied to PET film to form an interlayer insulating layer for multilayer printed circuit boards, to polyimide film to form a coverlay, or to copper foil to form resin-coated copper foil by coating and drying. Furthermore, by impregnating glass cloth, glass paper, carbon fiber, various nonwoven fabrics, etc., it can be used as a printed wiring board or a prepreg for CFRP. Furthermore, by using a photoradical initiator, it can also be used as a variety of resists.

[0047] Interlayer insulating layers, coverlays, resin-coated copper foils, prepregs, and the like containing the resin composition of the present invention can be heated and pressure-molded using a hot press or the like to form a cured product. [Example]

[0048] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0049] Synthesis Example 1 (Synthesis of polymer compound included in formula (1)) (Step 1) Synthesis of a copolymer (copolymer 1) represented by the following formula (5): A flask equipped with a thermometer, condenser, nitrogen gas inlet, and stirrer was charged with 38.5 parts of styrene, 1.5 parts of 4-hydroxyphenyl methacrylate, 0.4 parts of benzoyl peroxide, and 10 parts of propylene glycol monomethyl ether acetate (PGMEA). The mixture was reacted under a nitrogen atmosphere at 120-130°C for 5 hours to obtain a PGMEA solution of copolymer 1, represented by formula (5). A portion of the PGMEA solution was heated under reduced pressure to remove the solvent and unreacted styrene. The dry mass of copolymer 1 was calculated as the solids content, yielding 34.2 parts. Considering the 5.8 parts of unreacted styrene, the resulting copolymer was a copolymer of 32.7 parts of styrene and 1.5 parts of 4-hydroxyphenyl methacrylate. The number-average molecular weight of the sample used for the dry mass measurement was 38,000, and the weight-average molecular weight was 161,000. From the copolymerization ratio of styrene and 4-hydroxyphenyl methacrylate and the number average molecular weight, the value of n in formula (5) is calculated to be 361 and the value of m to be 9.

[0050] [ka]

[0051] (Step 2) Synthesis of a polymer compound (polymer compound 1) represented by the following formula (6): Unreacted styrene was distilled off together with PGMEA from the PGMEA solution of copolymer 1 obtained in step 1 under heating and reduced pressure, and then PGMEA was added to obtain 138 parts of a 25% by weight solution of copolymer 1. Five parts of triethylamine was added to this solution, and the solution temperature was raised to 60°C with stirring. Under this condition, 0.88 parts of methacrylic acid chloride was added and the reaction was continued for 1 hour. The reaction solution was pressure-filtered through a filter paper with a particle size of 1 μm to remove triethylamine hydrochloride. Excess triethylamine and PGMEA were distilled off from the filtrate using a rotary evaporator, and the amount of PGMEA was adjusted to obtain 139 parts of a solution containing 25% by weight of a polymer compound of the present invention (polymer compound 1) represented by formula (6) below. The number-average molecular weight of the obtained polymer compound 1 was 40,000, and the weight-average molecular weight was 164,000.

[0052] [ka]

[0053] Example 1 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 1.1 parts of N-phenylmaleimide were added and mixed uniformly to obtain resin composition 1 of the present invention.

[0054] Example 2 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 1.1 parts of acenaphthylene were added and mixed uniformly to obtain resin composition 2 of the present invention.

[0055] Example 3 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 0.3 parts of modified polyphenylene ether resin (SA-9000) were added and mixed uniformly to obtain resin composition 3 of the present invention.

[0056] Example 4 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 0.6 parts of modified polyphenylene ether resin (SA-9000) were added and mixed uniformly to obtain resin composition 4 of the present invention.

[0057] Example 5 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide and 0.38 parts of L-DAIC (manufactured by Shikoku Chemical Industry Co., Ltd.) were added as a radical initiator and mixed uniformly to obtain resin composition 5 of the present invention.

[0058] Example 6 (Preparation of Resin Composition of the Present Invention) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide and 0.38 parts of triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation) were added as a radical initiator and mixed uniformly to obtain resin composition 6 of the present invention.

[0059] Comparative Example 1 (Preparation of Comparative Resin Composition) To 10 parts of the PGMEA solution of polymer compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator was added and mixed uniformly to obtain a comparative resin composition 7.

[0060] (Evaluation of dielectric properties, glass transition temperature and linear expansion coefficient of cured resin composition) Resin compositions 1 to 7 obtained in Examples 1 to 6 and Comparative Example 1 were applied to the mirror surface of 18 μm-thick copper foil to a thickness of 280 μm using an applicator. The coating was then heated at 90°C for 10 minutes to dry off the solvent, yielding copper foil bearing a film-like adhesive made from the resin composition. The film-like adhesive on the copper foil thus obtained was then heat-cured at 180°C for 1 hour in a vacuum oven, and then immersed in an etching solution to remove the copper foil, yielding a 70 μm-thick cured film-like adhesive that could be handled as a film. The dielectric constant and dielectric loss tangent of the cured material at 10 GHz were measured by cavity resonance using a network analyzer 8719ET (Agilent Technologies). The glass transition temperature and α1 (linear expansion coefficient in the glassy region) of the cured material were also measured using a thermomechanical analyzer (TMA). The results are shown in Table 1.

[0061] (Evaluation of adhesive strength of cured resin composition) Using an applicator, resin compositions 1 to 7 obtained in Examples 1 to 6 and Comparative Example 1 were each applied to a 50 μm thickness on the matte side of a 12 μm-thick, low-roughness copper foil for high-frequency applications (CF-T4X-SV, manufactured by Fukuda Metal Foil & Powder Co., Ltd.). The coating was then heated at 90°C for 10 minutes to evaporate the solvent, yielding a copper foil bearing a film-like adhesive made from the resin composition of the present invention. The matte side of the same copper foil was then placed on the adhesive side of the resin-coated copper foil obtained above, and the resulting foil was heated and cured in a vacuum at a pressure of 3 MPa for 1 hour. The 90° peel strength (adhesion strength) between the copper foils was then measured using an Autograph AGX-50 (manufactured by Shimadzu Corporation). The results are shown in Table 1.

[0062] [Table 1]

[0063] As described above, the cured product of the resin composition of the present invention formed a flexible film and further exhibited excellent dielectric properties, heat resistance and adhesiveness.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R １ and R ２ each independently represent a hydrogen atom or a methyl group. m and n are the average values ​​of the number of repeating units and each independently range from 1 to 2,000. A resin composition comprising a polymer compound represented by the formula (I), a compound capable of radical polymerization with the polymer compound, and a radical initiator, wherein the compound capable of radical polymerization with the polymer compound is at least one selected from the group consisting of (A) a phenylmaleimide compound, (B) an acenaphthylene compound, (C) a modified polyphenylene ether resin having an unsaturated double bond at a terminal, and (D) an allyl isocyanurate compound.

2. 2. The resin composition according to claim 1, wherein the compound capable of undergoing radical polymerization with the polymer compound is a phenylmaleimide compound having one maleimide group in one molecule or a compound having one acenaphthylene structure in one molecule.

3. A film-like adhesive comprising the resin composition according to claim 1 or 2.

4. A cured product of the resin composition according to claim 1 or 2, or the film-like adhesive according to claim 3.

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