Curable resin composition, curable composition for metal-clad laminates, prepreg, resin film, metal-clad laminate, printed wiring board, and semiconductor package

Abstract

A curable resin composition including a resin (A1) in which the proportion of a polymerizable-group-containing compound (A) is 90 mass% or higher with respect to the total mass of resin components, wherein the polymerizable-group-containing compound (A) includes an indene ring, a vinylbenzyl group, and an arylalkyl group which is not vinylbenzyl.

Description

Curable resin compositions, curable compositions for metal-clad laminates, prepregs, resin films, metal-clad laminates, printed circuit boards, and semiconductor packages 【0001】 This disclosure relates to curable resin compositions, curable compositions for metal-clad laminates, prepregs, resin films, metal-clad laminates, printed circuit boards, and semiconductor packages. 【0002】 Metal-clad laminates, such as copper-clad laminates, prepregs that can be used for metal-clad laminates, and semiconductor packages using metal-clad laminates are used in a wide variety of electronic devices, including mobile communication devices such as smartphones, their base station equipment, network infrastructure equipment such as servers, routers, and large servers, large computers, personal computers, and industrial computers. They are also used in electronic devices installed in home appliances and automobiles. In particular, the demand for electronic communication equipment to process vast amounts of data at high speed is increasing due to the spread of 5G. 【0003】 In electronic devices, when processing vast amounts of data at high speed, substrate materials with low transmission loss in the high-frequency range are required. Low dielectric constant and low dielectric loss tangent resins are used as substrate materials to provide substrates with low transmission loss, but with the recent advancements in communication technology, there is a need for the development of resins with even lower dielectric constant and low dielectric loss tangent. 【0004】 Patent Document 1 discloses a curable vinylbenzyl compound having an indene ring structure into which vinylbenzyl groups are introduced, which can be used as a curable vinylbenzyl compound that has excellent low dielectric constant, low dielectric loss tangent, high heat resistance, and low water absorption. 【0005】 Japanese Patent Publication No. 2003-277440 【0006】 One of the objectives of this disclosure is to provide a curable resin composition with excellent heat resistance degradation in cured products, a curable composition for metal-clad laminates, a prepreg, a resin film, a metal-clad laminate, a printed circuit board, and a semiconductor package. 【0007】This disclosure includes, but is not limited to, the following embodiments. One embodiment relates to a curable resin composition in which the proportion of a polymerizable group-containing compound (A) to the total mass of the resin components is 90% by mass or more, and the polymerizable group-containing compound (A) comprises a resin (A1) containing an indene ring, a vinylbenzyl group, and an arylalkyl group other than a vinylbenzyl group. 【0008】 Another embodiment relates to a prepreg for metal-clad laminates, comprising a curable resin composition and a fibrous substrate, wherein the dielectric loss tangent (Df) (10 GHz, 25°C) of the cured product is 0.0015 or less, and the tensile strength of the cured product after being held at 240°C for 528 hours is 75% or more of the tensile strength of the cured product before heat treatment. 【0009】 This disclosure makes it possible to provide a curable resin composition with excellent heat degradation resistance in cured products, a curable composition for metal-clad laminates, a prepreg, a resin film, a metal-clad laminate, a printed circuit board, and a semiconductor package. 【0010】 The embodiments of the present invention will be described in detail below. The present invention is not limited to the embodiments described below. 【0011】 In this disclosure, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, the upper or lower limits of numerical ranges described in this disclosure may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain one or more of the corresponding substances unless otherwise specified. In this disclosure, the content of each component in the curable resin composition means the total amount of the multiple substances present in the curable resin composition if there are multiple substances corresponding to each component in the curable resin composition, unless otherwise specified. 【0012】In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by the following procedure. The weight average molecular weight and number average molecular weight are converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is approximated by a cubic equation using standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-20, F-80) (manufactured by Tosoh Corporation, trade name). The conditions of GPC are shown below. 【0013】 Apparatus: High-speed GPC apparatus "HLC-8320GPC" (manufactured by Tosoh Corporation, trade name) Detector: Ultraviolet absorption detector "UV-8320" (manufactured by Tosoh Corporation, trade name) Column: Guard column; TSKgel guardcolumn Super (HZ)-M+, Column; TSKgel SuperMultipore HZ-M (two), Reference column; TSKgel SuperH-RC (two) (all manufactured by Tosoh Corporation, trade name) Column size: 4.6 × 20 mm (guard column), 4.6 × 150 mm (column), 6.0 × 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1 mL Injection volume: 20 μL or 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40 °C 【0014】 A curable resin composition which is an embodiment of the present disclosure (hereinafter also referred to as "composition (1)") is a curable resin composition in which the ratio of the polymerizable group-containing compound (A) to the total mass of the resin components is 90% by mass or more, and the polymerizable group-containing compound (A) contains a resin (A1) containing an indene ring, a vinylbenzyl group, and an arylalkyl group other than the vinylbenzyl group. 【0015】In the present disclosure, the resin component of the composition (1) refers to a curable component and a thermoplastic elastomer. The curable component refers to a polymerizable group-containing compound (A) (hereinafter also referred to as "compound (A)") and a curable compound other than compound (A). Examples of the thermoplastic elastomer include polyether-based elastomers, styrene-based elastomers, conjugated diene-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and the like. These may be used alone or in combination of two or more. 【0016】 Examples of the curable compound other than the polymerizable group-containing compound (A) (hereinafter also referred to as "compound (A)") include epoxy resins, phenol resins, cyanate resins, benzoxazine resins, oxetane resins, amino resins, silicone resins, triazine resins, melamine resins, and the like. These may be used alone or in combination of two or more. 【0017】 In the composition (1), the ratio of compound (A) to the total mass of the resin component is 90% by mass or more. The ratio of compound (A) to the total mass of the resin component may further be 95% by mass or more, 98% by mass or more, or 100% by mass. 【0018】 Compound (A) includes a resin (A1) containing an indene ring, a vinylbenzyl group, and an arylalkyl group other than the vinylbenzyl group. As long as the resin (A1) contains an indene ring, a vinylbenzyl group, and an arylalkyl group other than the vinylbenzyl group in its molecular structure, there are no restrictions on other specific structures, molecular weights, etc., and a wide variety of resins can be used. The resin (A1) may be used alone or in combination of two or more. 【0019】Regarding the vinylbenzyl groups contained in resin (A1), the vinylbenzyl groups may be o-vinylbenzyl groups, m-vinylbenzyl groups, or p-vinylbenzyl groups. Among these, p-vinylbenzyl groups are preferred because they result in a resin with excellent dielectric properties in the cured product. The proportion of p-vinylbenzyl groups in the total vinylbenzyl groups contained in resin (A1) may be 10 mol% or more, 20 mol% or more, or 30 mol% or more. It may also be 100 mol% or less, 80 mol% or less, or 70 mol% or less. The proportion of p-vinylbenzyl groups in the total vinylbenzyl groups contained in resin (A1) may be in the range of 10 to 100 mol%. If the proportion of p-vinylbenzyl groups is less than 100 mol%, the remaining vinylbenzyl groups may be m-vinylbenzyl groups. 【0020】 Regarding arylalkyl groups other than vinylbenzyl groups contained in resin (A1) (hereinafter sometimes referred to as "arylalkyl groups"), the number of carbon atoms in the alkyl group within the arylalkyl group is not particularly limited, but may be in the range of 1 to 6, for example. Furthermore, the alkyl group may be linear or have a branched structure. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, etc. Among these, it is preferable that the alkyl group within the arylalkyl group has a relatively small number of carbon atoms, as this results in a resin with excellent dielectric properties. For example, the alkyl group within the arylalkyl group may be a methyl group or an ethyl group, or it may be a methyl group. 【0021】The aryl group in the arylalkyl group is not particularly limited as long as it is not a styryl group, and examples include a phenyl group, a naphthyl group, and structural parts having one or more substituents on their aromatic rings. Substituents on the aromatic ring include, for example, halogen atoms such as fluorine, chlorine, bromine, or iodine; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and isohexyl groups; alkoxy groups represented as RO- where R is one of the aforementioned alkyl groups; polymerizable unsaturated bond-containing groups such as vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyl, and (meth)acryloyloxy groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, and naphthyl groups; and aryloxy groups such as phenyloxy, tolyloxy, xylyloxy, mesityloxy, and naphthyloxy groups. 【0022】 The arylalkyl group may not have polymerizable unsaturated bonds. The aryl group in the arylalkyl group may be a phenyl group, a naphthyl group, and have one to three alkyl groups with 1 to 3 carbon atoms on their aromatic rings. 【0023】 The ratio of vinylbenzyl groups to the total number of vinylbenzyl groups and arylalkyl groups contained in resin (A1) may be 30 mol% or more, 60 mol% or more, or 85 mol% or more. It may also be 99 mol% or less, 95 mol% or less, or 80 mol% or less. The ratio of vinylbenzyl groups to the total number of vinylbenzyl groups and arylalkyl groups may be in the range of 30 to 99 mol%. 【0024】 In resin (A1), the vinylbenzyl group and arylalkyl groups other than the vinylbenzyl group may be directly bonded to the indene ring. An example of resin (A1) is a resin containing at least two compounds with different structures from the compounds represented by the following general formula (1), and R present in the resin. １ , R ２ and R３ at least one of which is a vinylbenzyl group, and RR present in the resin １ , R ２ and R ３ A resin (A1-1) in which at least one of them is an arylalkyl group other than a vinylbenzyl group can be mentioned. 【0025】 【0026】 [In General Formula (1), R １ , R ２ and R ３ are each independently a hydrogen atom, a vinylbenzyl group, or an arylalkyl group other than a vinylbenzyl group. R ４ is a hydrogen atom, a monovalent organic group, or a halogen atom, and all four R ４ may be different from each other, or two or more of the four R ４ may be the same as each other. ] 【0027】 R １ , R ２ and R ３ in General Formula (1) are each independently a hydrogen atom, a vinylbenzyl group, or an arylalkyl group other than a vinylbenzyl group. Details of the arylalkyl group other than the vinylbenzyl group are as described above. 【0028】 R ４The element is a hydrogen atom, a monovalent organic group, or a halogen atom. Examples of monovalent organic groups include alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, and isohexyl group; alkoxy groups represented as RO-, where R is one of the aforementioned alkyl groups; polymerizable unsaturated bond-containing groups, such as vinyl group, vinyloxy group, allyl group, allyloxy group, (meth)acryloyl group, and (meth)acryloyloxy group; aryl groups, such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group; and aryloxy groups, such as phenyloxy group, tolyloxy group, xylyloxy group, mesityloxy group, and naphthyloxy group. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine. R in general formula (1) ４ All of them may be hydrogen atoms. 【0029】 In resin (A1-1), R present in the resin １ , R ２ and R ３ At least one of them is a vinylbenzyl group, and at least one is an arylalkyl group. The resin (A1-1) is R in general formula (1). １ , R ２ and R ３ A compound in which one of the atoms is a vinylbenzyl group, one is an arylalkyl group, and one is a hydrogen atom, R １ , R ２ and R ３ A compound in which two of the groups are vinylbenzyl groups and one is an arylalkyl group, R １ , R ２ and R ３ A compound in which one of the groups is a vinylbenzyl group and the other two are arylalkyl groups, R １ , R ２ and R ３ A compound in which 1 to 3 of the groups are vinylbenzyl groups and the others are hydrogen atoms, R １ , R ２ and R ３ A compound in which one to three of the atoms are arylalkyl groups and the others are hydrogen atoms, R１ , R ２ and R ３ The compound may contain at least one compound in which all atoms are hydrogen atoms. In a compound having multiple arylalkyl groups in one molecule, the arylalkyl groups may all be different, or some or all of them may be the same. 【0030】 In resin (A1-1), the average of the total number of vinylbenzyl groups and arylalkyl groups in one molecule is preferably 1.5 or higher, more preferably 1.8 or higher, and particularly preferably 2.0 or higher, as this results in excellent curability. It may also be 3.0 or lower, 2.8 or lower, or 2.5 or lower. The average of the total number of vinylbenzyl groups and arylalkyl groups in one molecule may be in the range of 1.5 to 3.0. 【0031】 Furthermore, the ratio of vinylbenzyl groups to the total number of vinylbenzyl groups and arylalkyl groups contained in the resin (A1-1) may be 30 mol% or more, 60 mol% or more, or 85 mol% or more. It may also be 99 mol% or less, 95 mol% or less, or 80 mol% or less. The ratio of vinylbenzyl groups to the total number of vinylbenzyl groups and arylalkyl groups may be in the range of 30 to 99 mol%. 【0032】 The resin (A1-1) is identified by its molecular structure, and its manufacturing method is not particularly limited. One example of a method for producing resin (A1-1) is to react indene, styrene having a methyl halide group, and an aromatic compound having an alkyl halide corresponding to an arylalkyl group in the presence of a basic compound. 【0033】Examples of styrenes having a methyl halide group include o-chloromethylstyrene, m-chloromethylstyrene, and p-chloromethylstyrene. These may be used individually or in combination of two or more. Examples of aromatic compounds having an alkyl halide include α-chlorotoluene, α-chloroxylene, and 1-(chloromethyl)naphthalene. These may be used individually or in combination of two or more. 【0034】 The ratio of styrene having a methyl halide group to the total number of moles of styrene having a methyl halide group and aromatic compounds having an alkyl halide group may be 30 mol% or more, 60 mol% or more, or 85 mol% or more. It may also be 99 mol% or less, 95 mol% or less, or 80 mol% or less. The ratio of styrene having a methyl halide group to the total number of moles of styrene having a methyl halide group and aromatic compounds having an alkyl halide group may be in the range of 30 to 99 mol%. 【0035】 The total number of moles of styrene having a methyl halide group and an aromatic compound having an alkyl halide per mole of indene may be 1.5 moles or more, 1.8 moles or more, or 2.0 moles or more. It may also be 3.0 moles or less, 2.8 moles or less, or 2.5 moles or less. The total number of moles of styrene having a methyl halide group and an aromatic compound having an alkyl halide per mole of indene may be in the range of 1.5 to 3.0 moles. 【0036】 Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides. These may be used individually or in combination of two or more. 【0037】A phase-transfer catalyst may be used in the above reaction. Examples of phase transfer catalysts include quaternary ammonium salts such as tetra-n-butylammonium chloride, tetra-n-butylammonium bromide (tetra-n-butylammonium bromide), tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyldimethyltetradecylammonium chloride, tricaprylmethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, trioctylmethylammonium chloride, and tetra-n-butylammonium bisulfate; and quaternary phosphonium salts such as tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and benzyltriphenylphosphonium bromide. These may be used individually or in combination of two or more types. 【0038】 The above reaction may be carried out, for example, under heating and stirring conditions. The heating temperature may be around 50 to 100°C. The above reaction can also be carried out by solution polymerization. The solvent used is not particularly limited as long as it can dissolve the reaction raw materials and has a boiling point above the reaction temperature, but examples include aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene. These may be used individually or in combination of two or more. 【0039】Polymerization inhibitors may be used in the reaction system as needed. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, hydroquinone monomethyl ether, 1,4-benzoquinone, 2-t-butyl-1,4-benzoquinone, 2-t-butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-butylphenol, cresol, catechol, 4-t-butylcatechol, pyrogallol, and 4 Examples include methoxyphenol, thiodiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate. These may be used individually or in combination of two or more. 【0040】 The product obtained from the above reaction may be purified by known methods such as concentration, reprecipitation, and washing, if necessary. 【0041】 Another example of resin (A1) is a prepolymer (A1-2) obtained by polymerizing a portion of the vinyl groups in resin (A1-1). In this disclosure, a prepolymer is a polymer in which some of the polymerizable groups in the raw material remain without undergoing a polymerization reaction, and which has curability due to the remaining polymerizable groups. 【0042】 The prepolymer (A1-2) may be prepared by combining resin (A1-1) with other reaction materials other than resin (A1-1). The proportion of resin (A1-1) in the total monomer of the prepolymer (A1-2) may be 50 mol% or more, 80 mol% or more, or 100 mol%. 【0043】The method for producing the prepolymer (A1-2) is not particularly limited and can be produced by polymerizing reaction materials containing resin (A1-1) in a general manner. One example of this is radical polymerization. The polymerization initiator used in radical polymerization is not particularly limited and known ones such as azo polymerization initiators and organic peroxide polymerization initiators can be used. The polymerization reaction may be carried out in a solvent. Examples of solvents that can be used include toluene and xylene. These may be used individually or in combination of two or more. 【0044】 The weight-average molecular weight (Mw) of prepolymer (A1-2) is not particularly limited, but for example, from the viewpoint of ease of manufacture and ease of handling of the curable resin composition, it may be 1,000 or more, 2,000 or more, or 3,000 or more. It may also be 15,000 or less, 10,000 or less, or 8,000 or less. The weight-average molecular weight (Mw) of prepolymer (A2) may be in the range of 1,000 to 15,000. 【0045】 Examples of compounds (A) other than resin (A1) include compounds having a maleimide group, polyarylene ether compounds having a polymerizable group, aromatic compounds having a vinyl group, and triallyl isocyanurate. 【0046】 Examples of compounds having maleimide groups include bismaleimide compounds having two maleimide groups and maleimide resins. 【0047】Specific examples of bismaleimide compounds include, for example, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, and 3,3'-dimethyl-5,5'-die Tyl-4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3- Maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane , 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenoxy)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl ] sulfoxide, bis[4-(4-maleimidophenoxy)phenyl] sulfoxide, bis[4-(3-maleimidophenoxy)phenyl] sulfone, bis[4-(4-maleimidophenoxy)phenyl] sulfone, bis[4-(3-maleimidophenoxy)phenyl] ether, bis[4-(4-maleimidophenoxy)phenyl] ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethicone Rubenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene Examples include 1,3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, and aromatic bismaleimide compounds having an indane skeleton. 【0048】 Specific examples of maleimide resins include, for example, polyphenylmethane maleimide, maleimide resins having an indan skeleton, and biphenyl aralkyl type maleimide resins. 【0049】 Maleimide resins having an indan skeleton include, for example, those represented by the following general formula (2). 【0050】 [R in general formula (2)] ５[where a is a hydrogen atom or a methyl group, and a is an integer of 1 or more.] 【0051】 Examples of biphenylaralkyl-type maleimide resins include those represented by the following general formula (3). 【0052】 【0053】 [In general formula (3), b is an integer greater than or equal to 1.] 【0054】 Regarding polyarylene ether compounds having polymerizable groups, the arylene group is not particularly limited and examples include phenylene groups, naphthylene groups, and structures in which one or more alkyl groups, alkyloxy groups, halogen atoms, etc., are substituted on the aromatic carbons thereof. Examples of polymerizable groups include vinyl groups, vinyloxy groups, allyl groups, allyloxy groups, (meth)acryloyl groups, (meth)acryloyloxy groups, vinylbenzyl groups, vinylbenzyloxy groups, etc. Polyarylene ether compounds having polymerizable groups may have structural parts other than the polyarylene ether structure. Specifically, they may have acrylic polymerization sites, (poly)urethane sites, (poly)ester sites, etc., in the molecular chain. The number of polymerizable groups in one molecule of a polyarylene ether compound is not particularly limited, nor is the substitution position of the polymerizable groups particularly limited. For example, a polyarylene ether compound may have polymerizable groups at the molecular end, or it may have polymerizable groups at both ends. 【0055】 Specific examples of polyarylene ether compounds having polymerizable groups include, for example, the compound represented by the following general formula (4). 【0056】 【0057】 [In general formula (4), R ６ R is a hydrogen atom or a methyl group. ７ [x] is one of the following: vinylbenzyl group, acryloyl group, or methacryloyl group. c and d are integers of 1 or greater. X is a directly bonded or divalent organic group. 【0058】In general formula (4), X is a directly bonded divalent organic group, and its specific structure is not particularly limited, but examples include hydrocarbon groups having 1 to 6 carbon atoms, halogenated hydrocarbon groups, oxygen atoms, sulfur atoms, carbonyl groups, sulfonyl groups, etc. 【0059】 The molecular weight of the polyarylene ether compound having polymerizable groups is not particularly limited, but for example, the number average molecular weight (Mn) may be in the range of 1,000 to 5,000. 【0060】 Aromatic compounds having a vinyl group include, for example, styrene, divinylbenzene, and 1,2-bis(4-vinylphenyl)ethane. 【0061】 Among compounds (A) other than resin (A1), polyarylene ether compounds having polymerizable groups are preferred. Compound (A) may include resin (A1) as well as polyarylene ether compounds having polymerizable groups. 【0062】 The proportion of resin (A1) in compound (A) is arbitrary. For example, the proportion of resin (A1) to the total mass of compound (A) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more. It may also be 90% by mass or less, 70% by mass or less, or 60% by mass or less. The proportion of resin (A1) to the total mass of compound (A) may be in the range of 20 to 90% by mass. 【0063】 Furthermore, the proportion of resin (A1-1) in compound (A) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more. It may also be 90% by mass or less, 70% by mass or less, or 60% by mass or less. The proportion of resin (A1-1) to the total mass of compound (A) may be in the range of 20 to 90% by mass. 【0064】 Composition (1) may optionally contain various additives such as curing accelerators, polymerization inhibitors, flame retardants, silane coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, fillers, solvents, etc. Each of these may be used individually or in combination of two or more types. 【0065】 As a curing accelerator, for example, a radical polymerization initiator can be used. The radical polymerization initiator may be a thermal radical polymerization initiator or a photoradical polymerization initiator, but a thermal radical polymerization initiator is preferred. Specific examples of polymerization initiators include azo polymerization initiators and organic peroxide polymerization initiators. Examples of azo polymerization initiators include 2,2'-azobis(2,4,4-trimethylpentane), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1,1'-azobis(cyclohexane-1-carbonitride), and dimethyl-1,1'-azobis(1-cyclohexanecarboxylate). Examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropanenitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl4-cyanopentanoate). Examples of organic peroxide polymerization initiators include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, t-butyl perbenzoate, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, α,α'-di(t-butylperoxy)diisopropylbenzene, and t-butyl hydroperoxide. 【0066】 The content of the curing accelerator in composition (1) is not particularly limited, but for example, it may be 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, per 100 parts by mass of compound (A) total. Alternatively, it may be 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less. The content of the curing accelerator may be in the range of 0.05 to 10% by mass relative to the total mass of the resin components. 【0067】 Polymerization inhibitors include, for example, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, hydroquinone monomethyl ether, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, cresol, catechol, 4-tert-butylcatechol, pyrogallol, 4-methyl Examples include phenol or benzoquinone compounds such as toxyphenol; phenothiazine compounds such as phenothiazine, 3,7-dioctylphenothiazine, and 3,7-dicumylphenothiazine; and TEMPO compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate. The amount of polymerization inhibitor added may be, for example, in the range of 0.05 to 5% by mass relative to the total mass of the resin components. 【0068】 Examples of flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and inorganic flame retardants. The amount of flame retardant added is adjusted as appropriate depending on the type of flame retardant, the intended use of the curable composition, and the desired physical properties. For example, when using a phosphorus-based flame retardant, the amount may be adjusted by the phosphorus atom content in the curable composition. Specifically, the phosphorus atom content relative to the total mass of the resin components in composition (1), that is, the total mass of components other than the inorganic filler and solvent in composition (1), may be in the range of 0.1 to 20% by mass. 【0069】Silane coupling agents can be various compounds that are generally known. Examples of silane coupling agents include epoxy group-containing silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-n-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3- Examples include amino group-containing silanes such as aminopropyltrimethoxysilane; cationic silanes such as 3-(trimethoxylyl)propyltetramethylammonium chloride; vinyl group-containing silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acryloyl group-containing silanes such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; and mercapto group-containing silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. The content of the silane coupling agent is not limited to the above, but may be in the range of 0.5 to 5% by mass relative to the total mass of the resin components. 【0070】 Both organic and inorganic fillers can be used as fillers, but inorganic fillers are preferred. Examples of inorganic fillers include silica (SiO₂). ２ ), alumina (Al ２ O ３Examples of materials include titanium dioxide, barium titanate, strontium titanate, potassium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, aluminum borate, silicon carbide, mica, beryllia, clay, and talc. Among these, silica is preferred from the viewpoint of dielectric properties. The type of silica is not particularly limited and may be crystalline silica or amorphous silica, and may be natural silica or synthetic silica. The method of producing synthetic silica is also not particularly limited and may be wet silica such as colloidal silica, fumed silica (dry silica), or fused silica. The shape of silica is also not particularly limited and may be spherical silica, crushed silica, or solid silica, porous silica, or hollow silica. One type of filler may be used alone, or two or more types may be used in combination. As an example of combination, solid silica and hollow silica may be used in combination. The ratio of the two is not particularly limited, but for example, the ratio of hollow silica to the total mass of solid silica and hollow silica may be 1% by mass or more, 5% by mass or more, or 8% by mass or more. It may also be 50% by mass or less, 30% by mass or less, or 20% by mass or less. The ratio of hollow silica to the total mass of solid silica and hollow silica may be in the range of 1 to 50% by mass. 【0071】 The shape and size of the filler are not particularly limited. The average particle diameter of the filler may be, for example, 0.01 to 20 μm, or 0.1 to 10 μm. Here, the average particle diameter of the filler is the particle diameter at the point corresponding to 50% of the cumulative value in the volume-based particle distribution obtained by laser diffraction scattering. 【0072】 If composition (1) contains a filler, the amount of filler added may be in the range of 50 to 500 parts by mass per 100 parts by mass of the total resin components in composition (1). 【0073】 Composition (1) may be solvent-free or may contain a solvent. The solvent can adjust the viscosity of composition (1) to further improve its coating properties. Organic solvents are preferred as the solvent. 【0074】 Examples of organic solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. 【0075】 If composition (1) contains a solvent, the solid content of composition (1) may be, for example, in the range of 30 to 95% by mass. 【0076】 The method for producing composition (1) is not particularly limited. One example of a method for producing composition (1) is to blend and mix each component of composition (1). When mixing, each component may be blended and mixed as is, or any component may be dissolved or dispersed in a solvent before mixing. The mixing order of each component, temperature, time, and other conditions are not particularly limited and may be adjusted as appropriate according to the type of raw materials, production scale, production equipment, etc. 【0077】 [Prepreg] According to one embodiment, a prepreg containing composition (1) or a semi-cured product of composition (1) can be provided. This prepreg can be formed, for example, using composition (1) and a fibrous substrate. With respect to the semi-cured product of composition (1), in this disclosure, the state of B-stage in JIS K 6800 (1985) can be cited as one indicator of the semi-cured state. The prepreg may contain, for example, a hard composition (1) or a semi-cured product of composition (1) and a fibrous substrate such as a sheet-like fibrous substrate. In the prepreg, composition (1) may be in an uncured state, or composition (1) may be in a partially or entirely semi-cured state. 【0078】A prepreg can be obtained, for example, by impregnating a fibrous substrate with composition (1) and drying the fibrous substrate impregnated with composition (1). Drying is preferably carried out at a temperature above which volatile components such as solvents that may be contained in composition (1) are removed, and may also be carried out at a temperature above which the curable components contained in composition (1) are partially cured, depending on the application. Furthermore, it is preferable that the drying is adjusted so that the thermosetting resin contained in composition (1) is not completely cured. From this viewpoint, the drying temperature may be, for example, 80 to 200°C, and the drying time may be, for example, 1 to 30 minutes, depending on the drying temperature, drying apparatus, and its scale. 【0079】 The fibrous base material may be woven, knitted, or nonwoven fabric. The fibrous base material may be provided in the form of chopped strand mat, roving, etc. The fiber material may be either inorganic or organic fiber. Examples of inorganic fibers include glass fiber and carbon fiber. Examples of glass fiber include E glass, NE glass, D glass, S glass, and Q glass. Examples of organic fibers include polyimide, polyester, and tetrafluoroethylene. The fibrous base material may use one type of fiber alone, or two or more types in combination. From the viewpoint of dielectric properties and heat resistance, inorganic fibers are preferred for the fibrous base material, and glass fibers are more preferred. 【0080】 The fibrous substrate can be appropriately selected depending on the application of the prepreg, but a sheet-like fibrous substrate is preferred. The sheet-like fibrous substrate may be, for example, various sheet-like fibrous substrates used in known laminates for electrical insulating materials. The thickness of the sheet-like fibrous substrate is not particularly limited, but for example, 0.01 to 0.1 mm is preferred. Here, the thickness is determined by measuring the thickness at five points at equal distances across the entire surface of the sheet-like fibrous substrate and taking the arithmetic mean of the five points. 【0081】[Resin Film] According to one embodiment, a resin film comprising composition (1) or a semi-cured product of composition (1) can be provided. The resin film can be obtained, for example, by coating a material to be coated with composition (1) and drying or semi-curing it. Drying or semi-curing may be carried out in the same manner as the method for manufacturing the prepreg described above. After drying the resin film on the material to be coated, the product may be provided as a combination of the resin film and the material to be coated. For example, in this method, the resin film can be provided as a surface protective film, an interlayer insulating film, etc., in a printed circuit board. In another method, after drying the resin film on the material to be coated, the resin film may be peeled off the material to provide the resin film as a product. 【0082】 The material to be coated may be either an inorganic or organic substrate, and examples include glass substrates, metal foils, metal plates and other metal substrates, plastic plates, plastic films and other plastic substrates, paper substrates, and even fibrous substrates as described in the prepreg section above. In order to peel the resin film from the material to be coated and provide it, a material to be coated that has a release layer formed on its surface may be used. 【0083】 [Metal-clad laminate] According to one embodiment, a metal-clad laminate containing a cured product of composition (1) and a metal foil can be provided. With respect to the cured product, in this disclosure, the state of the C-stage in JIS K 6800 (1985) can be cited as one indicator of the cured product. 【0084】In a metal-clad laminate, the cured product of composition (1) may be included as the cured product of composition (1) itself, or it may be included in the form of a prepreg. The metal-clad laminate may include a prepreg layer and a metal foil placed on at least one surface of the prepreg layer. The prepreg layer is the cured product of the prepreg described above, and may consist of a single prepreg or multiple prepregs laminated together. Furthermore, the metal-clad laminate may have the metal foil placed on one surface of the cured product of composition (1) or the cured prepreg, or it may have the metal foil placed on both surfaces of the cured product of composition (1) or the cured prepreg. The metal-clad laminate may be manufactured by placing the metal foil on at least one surface of a single sheet-like prepreg, or by laminating two or more sheet-like prepregs and placing the metal foil on at least one surface of the outermost layer of the laminate. A metal-clad laminate may be manufactured by laminating two or more sheet-like prepregs and arranging metal foil on both sides of this laminate. 【0085】 The following describes a specific method for manufacturing metal-clad laminates, which involves arranging metal foil on a laminate of two or more sheet-like prepregs. 【0086】 First, two or more sheet-like prepregs are laminated to obtain a laminate. In this laminate, the two or more sheet-like prepregs may be identical, or some or all of them may be different. In the laminate, it is sufficient that at least one of the two or more sheet-like prepregs is obtained using the curable resin composition according to one embodiment. 【0087】Next, a metal foil is placed on at least one surface of the laminate. The laminate with the metal foil is then heated and pressurized. This causes the sheet-like prepreg to harden, and a hardened prepreg product can be obtained. Adjacent sheet-like prepregs can also be bonded together. The heating and pressurizing conditions are not particularly limited, but for example, the temperature can be 100 to 300°C, the time 10 to 300 minutes, and the pressure 0.5 to 50 MPa. After heating and pressurizing, reheating may be performed to further harden the prepreg. In this case, the reheating temperature can be 100 to 300°C. As for the pressurizing method, for example, an autoclave molding machine, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, etc., can be used. 【0088】 The metal used for the metal foil is not particularly limited and can include, for example, copper, nickel, aluminum, gold, silver, platinum, molybdenum, ruthenium, tungsten, iron, titanium, chromium, and alloys containing two or more of these metal elements. Industrially, it is preferable to use elemental copper, nickel, or aluminum. By using copper as the metal foil, a copper-clad laminate can be provided. 【0089】 [Printed Wiring Board] According to one embodiment, a printed wiring board containing a cured product of composition (1) can be provided. In the printed wiring board, the cured product of composition (1) may be included as the cured product of composition (1) itself, or it may be included in the form of a prepreg. The printed wiring board can be manufactured using composition (1), a prepreg, a metal-clad laminate, or a combination thereof. For example, a printed wiring board can be provided by forming wiring using a metal-clad laminate by a known method. Details of the prepreg and metal-clad laminate are as described above. The printed wiring board may be either a single-layer printed wiring board or a multi-layer printed wiring board. 【0090】[Semiconductor Package] According to one embodiment, a semiconductor package can be provided that includes a printed circuit board and a semiconductor element. More specifically, for example, a semiconductor package can be provided that includes a printed circuit board containing a cured product of composition (1) and a semiconductor element. The semiconductor package can be manufactured, for example, by mounting a semiconductor element, memory, etc., on a printed circuit board by a known method. 【0091】 One embodiment of a metal-clad laminate prepreg comprises a curable resin composition (hereinafter also referred to as "composition (2)") and a fibrous substrate, wherein the dielectric loss tangent (Df) of the cured product (10 GHz, 25°C) is 0.0015 or less, and the tensile strength of the cured product after being held at 240°C for 528 hours is 75% or more of the tensile strength of the cured product before heat treatment. 【0092】 Regarding the cured prepreg, in this disclosure, the state of the C-stage in JIS K 6800 (1985) can be cited as one indicator of the cured product. The cured prepreg may be manufactured in any way, but it can preferably be manufactured by the following procedure: 1. Stack multiple prepregs so that the thickness of the cured product is 0.6 mm ± 50 μm, and lay copper foil on both sides thereof. 3 ± 0.3 kg / cm ２ 1. Under vacuum pressing conditions, a double-sided copper-clad laminate is obtained by heating and pressurizing at 230±5°C for 80 minutes. 2. The double-sided copper-clad laminate obtained above is immersed in a 10% by mass aqueous solution of ammonium peroxide to remove the copper foil. 3. After removing the copper foil, the cured prepreg is dried at 105±5°C for 1 hour, and then left to stand for 24 hours in an ambient temperature of 24.2±1°C and humidity of 54±4% RH. 【0093】The size of the test specimen used to measure the dielectric loss tangent (Df) is not particularly limited, but for example, a 100 mm x 40 mm specimen can be used. The dielectric loss tangent (Df) can be measured in accordance with the split-post dielectric resonator method. The measuring device is not particularly limited, but for example, Agilent Technologies' "PNA Network Analyzer N5222B" can be used. The ambient temperature during measurement is 25°C, and the measurement conditions are 10 GHz. 【0094】 The size of the test specimen used to measure the tensile strength of the cured material is not particularly limited, but for example, a 230 mm x 25 mm test specimen can be used. If the fibrous substrate is directional, such as glass cloth, the test specimen is prepared by cutting it in the direction of the length of the fibers or at a 45° angle to the grid. The device used to measure tensile strength is not particularly limited, but for example, an Autograph from Shimadzu Corporation can be used. 【0095】 The dielectric loss tangent (Df) (10 GHz, 25°C) of the cured prepreg is 0.0015 or less. While there is no particular lower limit, it may be, for example, 0.0010 or higher. 【0096】 The retention rate of the tensile strength of the cured prepreg after being held at 240°C for 528 hours is 75% or higher. The upper limit is not particularly limited, but may be, for example, 100% or less, or 85% or less. 【0097】The composition (2) contained in the prepreg is not particularly limited as long as it can be cured by heating, but it is preferable, for example, to contain a polymerizable group-containing compound (B) as a curable component. One type of polymerizable group-containing compound (B) may be used alone, or two or more types may be used in combination. As an example of polymerizable group-containing compound (B), it is preferable to contain a compound (B1) with a relatively low molecular weight because it has high fluidity and allows for the incorporation of a larger amount of inorganic filler. By including a large amount of inorganic filler, it becomes easier to adjust the dielectric loss tangent (Df) of the cured product to 0.0015 or less. More specifically, it is preferable to contain a compound (B1) with a molecular weight of 1,000 or less. If compound (B1) is a resin having a molecular weight distribution, it is preferable that the number average molecular weight is 1,000 or less. The proportion of compound (B1) in 100 parts by mass of the total polymerizable group-containing compound (B) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more. Furthermore, the amount may be 90% by mass or less, 70% by mass or less, or 60% by mass or less. The proportion of compound (B1) in 100 parts by mass of the total polymerizable group-containing compound (B) may be in the range of 20 to 90% by mass. 【0098】 Another example of polymerizable group-containing compound (B) is compound (B2), which is preferable because it provides superior heat degradation resistance in the cured prepreg, and the functional group equivalent of the functional group that causes the curing reaction is 500 g / equivalent or less. The lower limit of the functional group equivalent is not particularly limited, but for example it may be 140 g / equivalent or more. The functional group equivalent of compound (B2) may be in the range of 140 to 500 g / equivalent. The ratio of compound (B2) to the total polymerizable group-containing compounds (B) may be 40% by mass or more, 50% by mass or more, 70% by mass or more, or 100% by mass. The ratio of compound (B2) to the total polymerizable group-containing compounds (B) may be in the range of 40 to 100% by mass. 【0099】In polymerizable group-containing compound (B), the functional group that causes the curing reaction is not particularly limited, and various compounds can be used. Examples of compounds that may contain a curable component include compounds having polymerizable unsaturated bond-containing groups such as vinyl groups, allyl groups, (meth)acryloyl groups, and maleimide groups. Compounds having a maleimide group may be combined with an amine compound to perform a curing reaction using a Michael addition reaction. In addition, compounds having an epoxy group may be used in combination with compounds known as epoxy curing agents, specifically phenolic resins, activated ester resins, amine compounds, etc. Among these, it is preferable to use one or more selected from the group consisting of compounds having a vinyl group, compounds having an allyl group, and compounds having a maleimide group, as this can further reduce the dielectric loss tangent in the cured prepreg, and compounds having a vinyl group are particularly preferred. 【0100】 The specific structure of the compound having a vinyl group is not particularly limited, but it is preferable that the vinyl group is included as a vinylbenzyl group, as this results in a compound with superior reactivity. The ratio of the compound containing a vinylbenzyl group (B3) to the total polymerizable group-containing compound (B) may be 40% by mass or more, 50% by mass or more, 70% by mass or more, or 100% by mass or more. The ratio of the compound containing a vinylbenzyl group (B3) to the total polymerizable group-containing compound (B) may be in the range of 40 to 100% by mass. 【0101】 Another example of polymerizable group-containing compound (B) is a compound (B4) containing an indene structure, which is preferable because it can further reduce the dielectric loss tangent in the cured prepreg. The ratio of compound (B4) to the total polymerizable group-containing compounds (B) may be 40% by mass or more, 50% by mass or more, 70% by mass or more, or 100% by mass or more. The ratio of compound (B4) to the total polymerizable group-containing compounds (B) may be in the range of 40 to 100% by mass. 【0102】As an example of a compound that falls under any of the above compounds (B1) to (B4), the aforementioned resin (A1-1) can be cited. Furthermore, examples of polymerizable group-containing compounds (B) other than resin (A1-1) include the aforementioned prepolymer (A1-2) and the various compounds described as specific examples of polymerizable group-containing compounds (A). 【0103】 Composition (2) may also contain other resin components besides polymerizable group-containing compound (B), such as curable compounds other than polymerizable group-containing compound (B), thermoplastic elastomers, etc. Examples of curable compounds other than polymerizable group-containing compound (B) include epoxy resins, phenolic resins, cyanate resins, benzoxazine resins, oxetane resins, amino resins, silicone resins, triazine resins, melamine resins, etc. These may be used individually or in combination of two or more. Examples of thermoplastic elastomers include polyether-based elastomers, styrene-based elastomers, conjugated diene-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, etc. These may be used individually or in combination of two or more. 【0104】 In composition (2), the composition of the resin components is not particularly limited as long as the dielectric loss tangent (Df) value and the tensile strength fiber retention rate after heat treatment of the cured prepreg are within the specified range. However, the ratio of polymerizable group-containing compound (B) to the total mass of the resin components may be 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass. 【0105】 Composition (2) may optionally contain various additives such as curing accelerators, polymerization inhibitors, flame retardants, silane coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, fillers, solvents, etc. Each of these may be used individually or in combination of two or more. Specific examples of these additives and their content in composition (2) are the same as those in composition (1). 【0106】Examples of fibrous substrates included in one embodiment of the prepreg include those exemplified above. Furthermore, a prepreg using composition (2) and the fibrous substrate can be manufactured in the same manner as described above. The ratio of composition (2) to the fibrous substrate in the prepreg is not particularly limited and can be adjusted as appropriate depending on the application of the prepreg. It is preferable that the proportion of curable resin material be in the range of 70 to 90% by mass, as this makes it easier to keep the dielectric loss tangent and tensile strength retention rate after heat treatment in the cured prepreg within the specified range. 【0107】 The prepreg of one embodiment can be used in applications such as metal-clad laminates, printed circuit boards, and semiconductor packages, similar to the prepreg using composition (1). 【0108】 Examples of embodiments are given below. The present invention is not limited to the following embodiments. <1> A curable resin composition in which the ratio of polymerizable group-containing compound (A) to the total mass of resin components is 90% by mass or more, and the polymerizable group-containing compound (A) comprises a resin (A1) containing an indene ring, a vinylbenzyl group, and an arylalkyl group other than a vinylbenzyl group. 【0109】 <2> The curable resin composition according to <1>, wherein the arylalkyl group other than the vinylbenzyl group does not have a polymerizable unsaturated bond. 【0110】 <3> The curable resin composition according to <1>, wherein the proportion of vinylbenzyl groups to the total number of moles of vinylbenzyl groups and arylalkyl groups other than vinylbenzyl groups contained in the resin (A1) is 30 mol% or more. 【0111】 <4> The resin (A1) contains at least two compounds that have different structures from the compounds represented by the following general formula (1), and R is present in the resin. １ , R ２ and R ３ At least one of them is a vinylbenzyl group, and RR present in the resin １ , R ２ and R ３The curable resin composition according to <1> above, comprising a resin (A1-1) in which at least one of the members is an arylalkyl group other than a vinylbenzyl group. 【0112】 【0113】 [In general formula (1), R １ , R ２ and R ３ Each of these is independently a hydrogen atom, a vinylbenzyl group, or an arylalkyl group other than a vinylbenzyl group. ４ is a hydrogen atom, a monovalent organic group, or a halogen atom, and has four R ４ All of them may be different from each other, and there are four R's. ４ Two or more of them may be identical. 【0114】 <5> The curable resin composition according to <4>, wherein in the resin (A1-1), the average of the total number of vinylbenzyl groups and arylalkyl groups other than vinylbenzyl groups in one molecule is 1.5 or more. 【0115】 <6> A prepreg comprising the curable resin composition described in any one of <1> to <5> above, or a semi-cured product of the curable resin composition. 【0116】 <7> A resin film comprising a curable resin composition according to any one of <1> to <5> above, or a semi-cured product of the curable resin composition. 【0117】 <8> A metal-clad laminate comprising a cured product of a curable resin composition described in any one of <1> to <5> above, or a cured product of a curable composition for metal-clad laminates described in <6> above, and a metal foil. 【0118】 <9> A printed circuit board comprising a cured product of any one of the curable resin compositions described in <1> to <5> above. 【0119】 <10> A semiconductor package comprising the printed circuit board described in <9> above and a semiconductor element. 【0120】 <11> A semiconductor package comprising a semiconductor element and a cured product of any one of <1> to <5> above for sealing the semiconductor element. 【0121】 <12> A printed circuit board comprising at least one of a surface protective film and an interlayer insulating film formed by any one of the curable resin compositions described in <1> to <5> above. 【0122】 <13> A prepreg for metal-clad laminates comprising a curable resin material and a fibrous substrate, wherein the dielectric loss tangent (Df) of the cured product (10 GHz, 25°C) is 0.0015 or less, and the tensile strength of the cured product after being held at 240°C for 528 hours is 75% or more of the tensile strength of the cured product before heat treatment. 【0123】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. 【0124】 Measurement Method for Weight-Average Molecular Weight (Mw) and Number-Average Molecular Weight (Mn) The weight-average molecular weight and number-average molecular weight were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-20, F-80) (manufactured by Tosoh Corporation, trade name). The GPC measurement conditions are shown below. 【0125】 Instrument: High-speed GPC instrument HLC-8320GPC (Tosoh Corporation, product name) Detector: Ultraviolet absorption detector UV-8320 (Tosoh Corporation, product name) Columns: Guard column; TSKgel guardcolumn Super(HZ)-M+, Column; TSKgel SuperMultipore HZ-M (2), Reference column; TSKgel SuperH-RC (2) (all Tosoh Corporation, product names) Column size: 4.6 × 20 mm (guard column), 4.6 × 150 mm (column), 6.0 × 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1 mL Injection volume: 20 μL or 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C 【0126】[Production of resin (A1-1)] A 500 mL reaction vessel equipped with a stirrer, thermometer, reflux tubing, and nitrogen inlet was charged with 35.6 parts by mass of indene, 124.9 parts by mass of chloromethylstyrene (*1), 6.5 parts by mass of α-chloro-p-xylene, 7.1 parts by mass of tetra-n-butylammonium bromide as a phase transfer catalyst, 0.1 parts by mass of phenothiazine as a polymerization inhibitor, and 94.5 parts by mass of toluene as a solvent. The mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 50 mL / min. 【0127】 Next, 125 parts by mass of a 48% sodium hydroxide aqueous solution was added dropwise over 20 minutes, and the mixture was stirred at 60°C for 9 hours. Nitrogen was continuously blown in during the reaction. After cooling to room temperature (25°C) and neutralizing with a 10% hydrochloric acid aqueous solution, the mixture was washed twice with pure water. After removing toluene by vacuum distillation, the resulting viscous liquid was washed with methanol and vacuum dried to obtain resin (A1-1). 【0128】 Chloromethylstyrene (*1): AGC Seimi Chemical Co., Ltd. "CMS-P", a mixture of m-isomer and p-isomer, m-isomer content approximately 50% by mass, p-isomer content approximately 50% by mass. 【0129】 [Example 1 and Comparative Example 1] Each component was blended in the proportions shown in Table 1, and the solid content was adjusted to approximately 65% ​​by mass with toluene to produce a curable resin composition. For components that are solutions in Table 1, the values ​​are based on solid content. The following evaluation tests were performed on the obtained curable resin compositions. The results are also shown in Table 1. 【0130】 Details of each component listed in Table 1 are as follows: • Resin (A1-1): Resin (A1-1) obtained earlier • Resin (A2): Polymerizable group-containing aromatic polyether compound, "HC-G0037" manufactured by JSR Corporation • Thermoplastic elastomer: Styrene-ethylene-butylene-styrene copolymer "ToughTec H1041" manufactured by Asahi Kasei Corporation • Curing accelerator: 2,2'-azobis(2,4,4-trimethylpentane), "VR-110" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Polymerization inhibitor: 2,2,6,6-tetramethyl-4-piperidyl-1-oxyl • Flame retardant: Phosphorus atom-containing compound represented by the following general formula ("Rabitol FP-72 (TP)" manufactured by Fushimi Pharmaceutical Co., Ltd.) 【0131】 【0132】 [e is an integer between 3 and 8.] 【0133】 • Silane coupling agent: 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-503" • Filler (1): Average particle size (D ５０ ) 1.0 μm solid silica filler (2): Average particle size (D ５０ ) 2.0 μm hollow silica 【0134】 [Prepreg Preparation] A curable resin composition was impregnated and coated onto glass cloth conforming to IPC standard #1078, and then heated and dried at 120°C for 10 minutes to obtain a prepreg. The solid content of the prepreg derived from the curable resin composition was approximately 80% by mass. 【0135】 [Preparation of Double-Sided Copper-Clad Laminates] Two layers of the obtained prepreg were prepared, and thirteen layers were prepared. On both sides of these, 18 μm thick electrolytic copper foil (SI-VSP-18, manufactured by Mitsui Mining & Smelting Co., Ltd.) was laid with the matte side facing the prepreg. This was then subjected to a load of 3 kg / cm². ２ A double-sided copper-clad laminate was obtained by heating and pressurizing under vacuum pressing conditions at 230°C for 80 minutes. 【0136】 [Evaluation of heat degradation resistance] A double-sided copper-clad laminate (with two layers of prepreg) was immersed in a copper etching solution (*2) to remove the copper foil from both sides. Two 230 mm x 25 mm test pieces were prepared by cutting the laminate at a 45° angle (diagonally) to the fiber direction of the glass cloth. One of the test pieces was heat-treated by leaving it at 240°C for 528 hours using a high-temperature dryer. Tensile tests were performed on both the untreated and heat-treated test pieces using a Shimadzu Autograph to measure their tensile strength. The tensile strength retention rate was calculated from the ratio of the measured values ​​of the heat-treated test piece to the measured values ​​of the untreated test piece, and this was evaluated as an indicator of heat degradation resistance. 【0137】 (*2) Copper etching solution: 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.) 【0138】[Evaluation of Dielectric Properties] A double-sided copper-clad laminate (with two layers of prepreg) was immersed in a copper etching solution (*2) to remove the copper foil from both sides, and a 100 mm x 40 mm test specimen was prepared. The obtained test specimen was dried at 105°C for 1 hour, and then left to stand for 24 hours in an ambient temperature of 24.2°C and a humidity of 54% RH. Next, the dielectric loss tangent (Df) was measured in the 10 GHz band at an ambient temperature of 25°C in accordance with the split-post dielectric resonator method. The measuring instrument used was the "PNA Network Analyzer N5222B" from agilent technologies. 【0139】 【0140】 As shown in Table 1, the curable resin composition of Example 1, in which the proportion of polymerizable group-containing compound (A) to the total mass of the resin components was 90% by mass or more, and compound (A) contained resin (A1), exhibited a retention rate of tensile strength of over 75% in the cured product after high-temperature, long-duration heat treatment, demonstrating excellent heat resistance to degradation in the cured product. On the other hand, Comparative Example 1, in which the proportion of polymerizable group-containing compound (A) to the total mass of the resin components was less than 90% by mass, exhibited a low retention rate of 46% in the cured product after high-temperature, long-duration heat treatment, indicating that it was prone to degradation by heat treatment. 【0141】 The disclosures of this application are related to the subject matter described in Japanese Patent Application No. 2024-217562, filed on 12 December 2024, the disclosures of which are incorporated herein by reference.

Claims

1. A curable resin composition in which the proportion of polymerizable group-containing compound (A) to the total mass of resin components is 90% by mass or more, and the polymerizable group-containing compound (A) comprises a resin (A1) containing an indene ring, a vinylbenzyl group, and an arylalkyl group other than a vinylbenzyl group.

2. The curable resin composition according to claim 1, wherein the arylalkyl group other than the vinylbenzyl group does not have a polymerizable unsaturated bond.

3. The curable resin composition according to claim 1, wherein the proportion of vinylbenzyl groups in the resin (A1) to the total number of moles of vinylbenzyl groups and arylalkyl groups other than vinylbenzyl groups is 30 mol% or more.

4. The resin (A1) contains at least two compounds having different structures among the compounds represented by the following general formula (1), and R present in the resin １ , R ２ and R ３ Among them, at least one is a vinylbenzyl group, and R present in the resin １ , R ２ and R ３ Among them, at least one is an arylalkyl group other than a vinylbenzyl group, and the curable resin composition according to claim 1 contains a resin (A1-1). [In general formula (1), R １ , R ２ and R ３ are each independently a hydrogen atom, a vinylbenzyl group, or an arylalkyl group other than a vinylbenzyl group. R ４ is a hydrogen atom, a monovalent organic group or a halogen atom, and all four R ４ may be different from each other, and two or more of the four R ４ may be the same as each other. ] 5. The curable resin composition according to claim 4, wherein in the resin (A1-1), the average of the total number of vinylbenzyl groups and arylalkyl groups other than vinylbenzyl groups in one molecule is 1.5 or more.

6. A prepreg comprising a curable resin composition according to any one of claims 1 to 5 or a semi-cured product of the curable resin composition.

7. A resin film comprising a curable resin composition according to any one of claims 1 to 5 or a semi-cured product of the curable resin composition.

8. A metal-clad laminate comprising a cured product of a curable resin composition according to any one of claims 1 to 5 and a metal foil.

9. A printed circuit board comprising a cured product of a curable resin composition according to any one of claims 1 to 5.

10. A semiconductor package comprising a printed circuit board according to claim 9 and a semiconductor element.

11. A semiconductor package comprising a semiconductor element and a cured product of a curable resin composition according to any one of claims 1 to 5 for encapsulating the semiconductor element.

12. A printed circuit board comprising at least one of a surface protective film and an interlayer insulating film formed by the curable resin composition according to any one of claims 1 to 5.

13. A prepreg for metal-clad laminates comprising a curable resin composition and a fibrous substrate, wherein the dielectric loss tangent (Df) (10 GHz, 25°C) of the cured product is 0.0015 or less, and the tensile strength of the cured product after being held at 240°C for 528 hours is 75% or more of the tensile strength of the cured product before heat treatment.

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