Curable composition, prepreg, metal-clad laminate, printed wiring board and semiconductor package

Abstract

To provide a curable composition, a prepreg, a metal-clad laminate, a printed wiring board and a semiconductor package having excellent homogeneity of a cured product.SOLUTION: There is provided a curable composition comprising a compound (A) having a vinylbenzyl group and a compound (B) having a 2,2,6,6-tetramethylpiperidine structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a curable composition, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor package. [Background technology]

[0002] Metal-clad laminates, such as copper-clad laminates, prepregs that can be used with metal-clad laminates, and semiconductor packages that use metal-clad laminates are used in a variety of electronic devices, such as mobile communication devices such as smartphones, their base station equipment, network infrastructure devices such as servers, routers, and large servers, large computers, personal computers, industrial computers, etc. They are also used in electronic devices installed in home appliances, automobiles, etc.

[0003] When electronic devices process huge amounts of data at high speed, they require circuit board materials with low transmission loss in the high-frequency range. While resins with low dielectric constants and low dielectric loss tangents are used as circuit board materials and provide circuit boards with low transmission loss, recent advances in communication technology have created a demand for the development of resins with even lower dielectric constants and dielectric loss tangents.

[0004] Patent Document 1 discloses a compound having an indene ring structure into which a vinylbenzyl group has been introduced, as a curable vinylbenzyl compound that can give a cured product excellent in dielectric properties, high heat resistance, and low water absorption. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-277440 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide a curable composition, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor package that produce cured products with excellent homogeneity. [Means for solving the problem]

[0007] The present disclosure includes the following embodiments: The present disclosure is not limited to the following embodiments. One embodiment relates to a curable composition comprising a compound (A) having a vinylbenzyl group and a compound (B) having a 2,2,6,6-tetramethylpiperidine structure. [Effects of the Invention]

[0008] The present disclosure makes it possible to provide a curable composition, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor package that have excellent uniformity in the cured product. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a field emission scanning electron microscope photograph of the cross section of the copper clad laminate obtained in Example 1. [Figure 2] FIG. 2 is a field emission scanning electron microscope photograph of a cross section of the copper clad laminate obtained in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0011] In the present disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, the upper or lower limit of a numerical range described in the present disclosure may be replaced with a value shown in an example. In the present disclosure, unless otherwise specified, each component may contain one or more of the corresponding substances. In the present disclosure, when a plurality of substances corresponding to each component are present in the curable composition, the content of each component in the curable composition means the total amount of the plurality of substances present in the curable composition, unless otherwise specified.

[0012] In this disclosure, the weight-average molecular weight and number-average molecular weight are values ​​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 (Types: A-2500, A-5000, F-20, F-80) manufactured by Tosoh Corporation). The GPC conditions are shown below.

[0013] Apparatus: High-speed GPC apparatus "HLC-8320GPC" (Tosoh Corporation, product name) Detector: Ultraviolet absorption detector "UV-8320" (Tosoh Corporation, product name) Columns: Guard column: TSKgel guard column Super(HZ)-M+, columns: TSKgel SuperMultipore HZ-M (2 columns), reference column: TSKgel SuperH-RC (2 columns) (all products of Tosoh Corporation) Column dimensions: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: tetrahydrofuran Sample concentration: 10mg / 1mL Injection volume: 1μL Flow rate: 0.35mL / min Measurement temperature: 40℃

[0014] A curable composition that is one embodiment of the present disclosure is a curable composition that includes a compound (A) having a vinylbenzyl group and a compound (B) having a 2,2,6,6-tetramethylpiperidine structure.

[0015] Regarding compound (A) containing a vinylbenzyl group (hereinafter, sometimes referred to as "compound (A)"), the vinylbenzyl group is a hydrocarbon group with low polarity, making it a preferred functional group from the perspective of the dielectric properties of the cured product. Furthermore, because the vinylbenzyl group is particularly reactive among radically polymerizable groups, compound (A) is characterized by excellent fast-cure properties. On the other hand, compounds containing highly reactive functional groups such as the vinylbenzyl group are difficult to control the polymerization reaction, and the cured product tends to be nonuniform, a tendency that becomes particularly pronounced when used in combination with other resin materials, inorganic fillers, etc. Furthermore, when this compound is used in prepreg applications, the rapid progression of the polymerization reaction can reduce the impregnation of glass cloth.

[0016] Without being bound by any particular theory, according to one embodiment of the present disclosure, by adding a compound (B) having a 2,2,6,6-tetramethylpiperidine structure (hereinafter, sometimes referred to as "compound (B)") to a curable composition containing compound (A), compound (B) acts as a radical scavenger, controlling the progress of the polymerization reaction. As a result, even when compound (B) is used in combination with other resin materials or inorganic fillers, it is possible to obtain a highly homogeneous cured product, and it is also thought that the impregnation of glass cloth is also inhibited.

[0017] The compound (A) having a vinylbenzyl group is not limited in terms of its specific structure or molecular weight, and a wide variety of compounds can be used, as long as they have one or more vinylbenzyl groups in one molecule. One type of compound (A) may be used alone, or two or more types may be used in combination.

[0018] Specific examples of the compound (A) include a compound represented by the following general formula (2) (hereinafter, this may be referred to as "compound (A1)"), a prepolymer using the compound (A1) (hereinafter, this may be referred to as "prepolymer (A2)"), and a compound represented by the following general formula (3) (hereinafter, this may be referred to as "compound (A3)"):

[0019] [ka]

[0020] [In general formula (2), Ar 1 represents an aromatic hydrocarbon structure which may have a substituent, and k is an integer of 1 or 2 or more.

[0021] [ka]

[0022] [In general formula (3), Ar 2 represents an aromatic hydrocarbon structure which may have a substituent. 3 represents an aryl group other than a styryl group, l is an integer of 1 or 2 or more, and m is an integer of 1 or 2 or more.

[0023] In the compound represented by the above general formula (2) (compound (A1)), the vinylbenzyl group contained in compound (A1) may be any of o-vinylbenzyl, m-vinylbenzyl, or p-vinylbenzyl. Among these, p-vinylbenzyl is preferred. The proportion of p-vinylbenzyl groups in all vinylbenzyl groups contained in the vinylbenzyl compound may be 10% or more, 20% or more, or 30% or more. It may also be 100% or less, 80% or less, or 70% or less. For example, it may be in the range of 10 to 100%. When the proportion of p-vinylbenzyl groups is less than 100%, the remaining vinylbenzyl groups may be m-vinylbenzyl groups.

[0024] Ar in general formula (2) 1 is an aromatic hydrocarbon structure which may have a substituent. Specific examples of aromatic hydrocarbons include benzene, indene, indane, naphthalene, fluorene, anthracene, phenanthrene, tetracene, chrysene, pyrene, and triphenylene. Among these, benzene, indene, naphthalene, and fluorene are preferred, indene and fluorene are more preferred, and indene is particularly preferred.

[0025] Ar 1 When has a substituent, specific examples thereof include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a t-butyl group; unsaturated bond-containing groups such as a vinyl group and an allyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthyl group; aryloxy groups such as a phenyloxy group, a tolyloxy group, a xylyloxy group, a mesityloxy group, and a naphthyloxy group; aralkyl groups such as a benzyl group, an α-methylbenzyl group, a triphenylmethyl group, and a naphthylmethyl group; and aralkyloxy groups such as a benzyloxy group. 1 may have no substituent.

[0026] In the general formula (2), k is an integer of 1 or 2 or more. A preferred number of k is Ar 1 Although it depends on the type of aromatic hydrocarbon structure represented by Ar 1 When Ar is an indene ring structure, k is preferably an integer of 1 to 3. 1 When is an indene ring structure, examples of the compound (A1) include compounds represented by the following general formula (2-1).

[0027] [ka]

[0028] [In general formula (2-1), R 2 , R 3 and R 4 is a vinylbenzyl group or a hydrogen atom, and R 2 , R 3 and R 4 At least one of the groups is a vinylbenzyl group.

[0029] When a compound represented by general formula (2-1) is used as compound (A1), one type may be used alone, or multiple types of compounds having different numbers of vinylbenzyl groups per molecule may be used. In the latter case, the compound will have excellent curability, so the average number of vinylbenzyl groups per molecule is preferably in the range of 1.0 to 3.0, more preferably 1.6 to 2.5.

[0030] The compound (A1) is a compound specified by its molecular structure, and its production method is not particularly limited. 1 The compound can be produced by reacting an aromatic compound corresponding to the group with styrene having a halogenated methyl group in the presence of a basic compound.

[0031] Examples of styrenes having a halogenated methyl group include o-chloromethylstyrene, m-chloromethylstyrene, and p-chloromethylstyrene. One type of styrene having a halogenated methyl group may be used alone, or two or more types may be used in combination. Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides. One type of basic compound may be used alone, or two or more types may be used in combination.

[0032] A phase transfer catalyst may be used in the above reaction. Examples of the phase transfer catalyst 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 hydrogen sulfate; and quaternary phosphonium salts such as tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and benzyltriphenylphosphonium bromide.

[0033] Ar 1The reaction of an aromatic compound corresponding to the group with a styrene having a halogenated methyl group and a basic compound can be carried out by solution polymerization. The reaction may be carried out, for example, under heating and stirring conditions. If necessary, a polymerization inhibitor may be added to the reaction system. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 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, and pyrogallol. phenol or benzoquinone compounds such as 4-methoxyphenol; phenothiazine compounds such as phenothiazine, 3,7-dioctylphenothiazine, and 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, bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl)sebacate, etc. The obtained product may be purified, if necessary, by known methods such as concentration, reprecipitation, and washing.

[0034] The amount of polymerization inhibitor added is, for example, Ar 1 The content may be in the range of 0.05 to 5% by mass relative to 100 parts by mass of the total of the aromatic compound corresponding to the group and the styrene having a halogenated methyl group.

[0035] The obtained product may be a single compound or a mixture of two or more compounds. When the product is a mixture of two or more compounds, it may contain a compound in which k in the general formula (2) is 0, and the mixture may be used as is in the curable composition. In this case, the average number of vinylbenzyl groups per molecule in the mixture is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.6 to 2.5, in order to obtain a curable composition with excellent curability.

[0036] In the present disclosure, the term "prepolymer (A2)" refers to a polymer in which some of the polymerizable reactive groups of the monomer, which is the raw material of the polymer, remain. Therefore, the prepolymer (A2) has unreacted vinylbenzyl groups derived from the compound (A1) and exhibits radical polymerizability.

[0037] The prepolymer (A2) may contain, in addition to the compound (A1), other monomers other than the compound (A1). The proportion of the compound (A1) in the total monomers constituting the prepolymer (A2) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.

[0038] The method for producing the prepolymer (A2) is not particularly limited, and it can be produced by a method in which a monomer containing the compound (A1) is polymerized by a general method, one example of which is radical polymerization.

[0039] The polymerization initiator used in the radical polymerization is not particularly limited, and examples thereof include azo-based polymerization initiators and organic peroxide-based polymerization initiators. Examples of azo-based 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-carbonitrile), and dimethyl 1,1'-azobis(cyclohexane-1-carbonitrile). , 1'-azobis(1-cyclohexanecarboxylate), 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), 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 4-cyanopentanoate), and the like. Examples of organic peroxide polymerization initiators include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, bis(tert-butylperoxyisopropyl)benzene, and tert-butyl hydroperoxide.

[0040] The radical polymerization initiator may be used alone or in combination of two or more. The amount of radical polymerization initiator used can be adjusted appropriately depending on the desired degree of polymerization, etc., but is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the total of the monomers that are the reaction raw materials, in order to facilitate reaction control.

[0041] The polymerization reaction of the prepolymer (A2) may be carried out in a solvent. Examples of the solvent include toluene and xylene. These may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is preferably in the range of 30 to 500 parts by mass per 100 parts by mass of the total of the monomers, which are the reaction raw materials, in order to facilitate reaction control.

[0042] The weight-average molecular weight (Mw) of the prepolymer (A2) is not particularly limited, but is preferably in the range of 50,000 to 400,000, from the viewpoint of ease of production and ease of handling of the curable composition. The weight-average molecular weight (Mw) of the prepolymer (A2) may be 70,000 or more, 80,000 or more, or 100,000 or more. It may also be 300,000 or less, 250,000 or less, or 200,000 or less.

[0043] Regarding the compound represented by the above general formula (3) (compound (A3)), the vinylbenzyl group contained in compound (A3) may be any of o-vinylbenzyl group, m-vinylbenzyl group, and p-vinylbenzyl group. Among these, p-vinylbenzyl group is preferred. The proportion of p-vinylbenzyl groups in all vinylbenzyl groups contained in the vinylbenzyl compound may be 10% or more, 20% or more, or 30% or more. It may also be 100% or less, 80% or less, or 70% or less. For example, it may be in the range of 10 to 100%. When the proportion of p-vinylbenzyl groups is less than 100%, the remaining vinylbenzyl groups may be m-vinylbenzyl groups.

[0044] Ar in general formula (3) 3 is an aryl group other than a styryl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthyl group.

[0045] Ar in general formula (3) 2is an aromatic hydrocarbon structure which may have a substituent. Specific examples of aromatic hydrocarbons include benzene, indene, naphthalene, fluorene, anthracene, phenanthrene, tetracene, chrysene, pyrene, and triphenylene. Among these, benzene, indene, naphthalene, and fluorene are preferred, indene and fluorene are more preferred, and indene is particularly preferred.

[0046] Ar 2 When Ar has a substituent, specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl; unsaturated bond-containing groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, and naphthyl; and aryloxy groups such as phenyloxy, tolyloxy, xylyloxy, mesityloxy, and naphthyloxy. 2 may have no substituent.

[0047] In the general formula (3), l is an integer of 1 or 2 or more, and m is an integer of 1 or 2 or more. Preferred numbers for l and m are Ar 2 Although it depends on the type of aromatic hydrocarbon structure represented by Ar 2 When Ar is an indene ring structure, l and m are each preferably an integer of 1 to 3. Furthermore, the sum of l and m is more preferably 2 or 3. 2 When is an indene ring structure, examples of the compound (A3) include compounds represented by the following general formula (3-1).

[0048] [ka]

[0049] [In general formula (3-1), R 5 , R 6 and R 7 is either a vinylbenzyl group, an arylmethyl group, or a hydrogen atom. 5 , R 6 and R7 At least one of the groups is a vinylbenzyl group and at least one of the groups is an arylmethyl group.

[0050] When a compound represented by general formula (3-1) is used as compound (A3), one type may be used alone, or a plurality of types of compounds having different molecular structures may be used.

[0051] The compound (A3) is a compound specified by its molecular structure, and its production method is not particularly limited. 2 Aromatic compounds corresponding to the group, styrene with halogenated methyl groups, and Ar 3 The compound (A1) can be produced by reacting an aromatic compound having a halogenated methyl group corresponding to the group in the presence of a basic compound. The reaction conditions are the same as those described for the production method of compound (A1).

[0052] Examples of styrenes having a halogenated methyl group include o-chloromethylstyrene, m-chloromethylstyrene, and p-chloromethylstyrene. One type of styrene having a halogenated methyl group may be used alone, or two or more types may be used in combination. Ar 3 Examples of aromatic compounds having a halogenated methyl group corresponding to the group include α-chlorotoluene and α-chloro-p-xylene. Aromatic compounds having a halogenated methyl group may be used alone or in combination of two or more. Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides. A basic compound may be used alone or in combination of two or more.

[0053] The obtained product may be a single compound or a mixture of two or more compounds. In the case of a mixture of two or more compounds, it may partially contain a compound in which either or both of l and m in the above general formula (3) are 0, and the mixture may be used as it is in the curable composition.

[0054] The compound (B) having a 2,2,6,6-tetramethylpiperidine structure is not limited in terms of its specific structure or molecular weight, and a wide variety of compounds can be used, as long as it has one or more 2,2,6,6-tetramethylpiperidine structures (hereinafter sometimes referred to as "TMP structures") in one molecule. One type of compound (B) may be used alone, or two or more types may be used in combination.

[0055] Among the compounds (B), compounds having two or more TMP structures in one molecule are preferred because they are more effective in improving the uniformity of the cured product.

[0056] Among the compounds (B), examples of compounds having one TMP structure per molecule include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-cyclohexylcarbonyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

[0057] Among the compounds (B), examples of compounds having two or more TMP structures in one molecule include a compound represented by the following general formula (1) (hereinafter, this may be referred to as "compound (B1)").

[0058] [ka]

[0059] [In general formula (1), R 1 represents an organic group, and n is an integer of 2 or more.

[0060] In general formula (1), n ​​is an integer of 2 or more. The upper limit of n is not particularly limited, but from the viewpoint of miscibility with the curable composition, it is preferably 4 or less, more preferably 3 or less, and particularly preferably 2.

[0061] R in general formula (1) 1 represents an organic group. 1 Although the hydrocarbon group may contain elements other than carbon and hydrogen as part of its structure, it is preferably a hydrocarbon group from the viewpoint of the dielectric properties of the cured product of the curable composition. Specific examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic ring-containing hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is not particularly limited, but from the viewpoints of miscibility with the curable composition and the effect of improving the homogeneity of the cured product, it is preferably 4 or more, more preferably 6 or more. It is also preferably 20 or less, more preferably 16 or less, and particularly preferably 12 or less. The number of carbon atoms in the hydrocarbon group may be, for example, in the range of 4 to 20.

[0062] Among the compounds (B1), a particularly preferred example is one represented by the following general formula (1-1).

[0063] [ka]

[0064] [In general formula (1-1), p is an integer of 4 to 20.]

[0065] The curable composition according to one embodiment of the present disclosure is only required to contain the compound (A) and the compound (B), and the contents thereof are not particularly limited.

[0066] Regarding the blending ratio of compound (A) and compound (B), the ratio of compound (B) to the total mass of compound (A) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, since this more significantly enhances the effect of obtaining a highly homogeneous cured product. Furthermore, the ratio of compound (B) to the total mass of compound (A) is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The ratio of compound (B) to the total mass of compound (A) may be, for example, in the range of 0.05 to 5% by mass. Note that when a polymerization inhibitor equivalent to compound (B) is used during the production of compound (A), the blending ratio of compound (A) to compound (B) is calculated without including the amount used during the production.

[0067] When a polymerization inhibitor corresponding to compound (B) is used during the production of compound (A), the amount of compound (B) actually contained in the curable composition is the sum of the amount used during the production of compound (A) and the amount newly added. In this case, taking into account the amount of polymerization inhibitor that can be added during the production of compound (A), the ratio of compound (B) to the total mass of compound (A) may be, for example, 0.1% by mass or more, 0.15% by mass or more, or 0.25% by mass or more. It may also be 10% by mass or less, 6% by mass or less, or 5.5% by mass or less.

[0068] The curable composition may contain other components in addition to the compound (A) and the compound (B) as necessary. Examples of the other components include a radically polymerizable compound (C) other than the compound (A), a thermosetting compound other than the radically polymerizable compound, an elastomer, a polymerization initiator, a flame retardant, a coupling agent, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, a filler, a solvent, etc. Each of the other components may be used alone, or two or more may be used in combination.

[0069] Specific examples of other radically polymerizable compounds (C) (hereinafter sometimes referred to as "compound (C)") include compounds having a maleimide group, polyarylene ether compounds having a radically polymerizable group, styrene, divinylbenzene, triallyl isocyanurate, etc.

[0070] Examples of compounds having a maleimide group include compounds having one or more N-substituted maleimide groups and derivatives thereof.

[0071] Examples of compounds having one or more N-substituted maleimide groups include aromatic maleimide compounds, which are compounds having an N-substituted maleimide group directly bonded to an aromatic ring; aromatic bismaleimide compounds, which are compounds having two N-substituted maleimide groups directly bonded to an aromatic ring; aromatic polymaleimide compounds, which are compounds having three or more N-substituted maleimide groups directly bonded to an aromatic ring; and aliphatic maleimide compounds, which are compounds having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0072] Specific examples of the compound having one or more N-substituted maleimide groups include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, 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, 3,3'-dimethyl-5, 5'-Diethyl-4,4'-diphenylmethane bismaleimide, 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 Pan, 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-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis 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-dimethylbenzyl]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, 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, polyphenylmethane maleimide, aromatic bismaleimide compounds having an indane skeleton, biphenylaralkyl maleimide compounds, etc.

[0073] Examples of derivatives of compounds having one or more N-substituted maleimide groups include aminomaleimide compounds containing structural units derived from the above-mentioned compounds having one or more N-substituted maleimide groups and structural units derived from diamine compounds.

[0074] Regarding the polyarylene ether compound having a radical polymerizable group, the arylene group is not particularly limited, and examples thereof include a phenylene group, a naphthylene group, and structures in which one or more alkyl groups, alkyloxy groups, halogen atoms, etc. are substituted on the aromatic carbon of these groups. Examples of the radical polymerizable group include a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, a vinylbenzyl group, and a vinylbenzyloxy group. The polyarylene ether compound having a radical polymerizable group may have a structural moiety other than the polyarylene ether structure. Specifically, the molecular chain may contain an acrylic polymerization moiety, a (poly)urethane moiety, a (poly)ester moiety, etc. The number of radical polymerizable groups in one molecule of the polyarylene ether compound is not particularly limited, and the substitution position of the radical polymerizable group is also not particularly limited. For example, the polyarylene ether compound may have a radical polymerizable group at the molecular terminal, or may have a radical polymerizable group at both terminals.

[0075] Specific examples of polyarylene ether compounds having a radical polymerizable group include compounds represented by the following general formula (4).

[0076] [ka]

[0077] [In general formula (4), R 8 is a hydrogen atom or a methyl group; s and t are integers of 1 or greater; and X is a divalent organic group.

[0078] X in general formula (4) is a divalent organic group, and the specific structure is not particularly limited, but examples thereof include a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group, an oxygen atom, a sulfur atom, a carbonyl group, and a sulfonyl group.

[0079] The molecular weight of the polyarylene ether compound having a radical polymerizable group is not particularly limited, but the number average molecular weight (Mn) may be in the range of 1,000 to 5,000, for example.

[0080] When the curable composition contains compound (C), the ratio of compound (B) to the total mass of compound (A) and compound (C) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and particularly preferably 0.1 mass% or more. Furthermore, the ratio of compound (B) to the total mass of compound (A) and compound (C) is preferably 5 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less. The ratio of compound (B) to the total mass of compound (A) and compound (C) may be, for example, in the range of 0.01 to 5 mass%.

[0081] When the curable composition contains the compound (C), the ratio of the compound (A) to the compound (C) is arbitrary. For example, the ratio of the compound (A) to the total mass of the compounds having a radical polymerizable group in the curable composition may be 10% by mass or more, 20% by mass or more, or 30% by mass or more. It may also be 80% by mass or less, 70% by mass or less, or 60% by mass or less. The ratio of the compound (A) to the total mass of the compounds having a radical polymerizable group may be, for example, in the range of 10 to 80% by mass.

[0082] Examples of other thermosetting compounds include epoxy resins, phenolic resins, cyanate resins, benzoxazine resins, oxetane resins, amino resins, silicone resins, triazine resins, and melamine resins. The proportion of compound (A) relative to the total mass of the curable components in the curable composition may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 100% by mass. It may also be 80% by mass or less, 70% by mass or less, or 60% by mass or less. The proportion of compound (A) relative to the total mass of the curable components may be, for example, in the range of 10 to 100% by mass.

[0083] Examples of the elastomer include polyether elastomers, styrene elastomers, conjugated diene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.

[0084] The weight average molecular weight (Mw) of the elastomer is not particularly limited and may be, for example, 100,000 or less, 60,000 or less, or 30,000 or less. It may also be 1,000 or more, 3,000 or more, or 5,000 or more. The weight average molecular weight (Mw) of the elastomer may be, for example, in the range of 1,000 to 100,000.

[0085] When the curable composition contains an elastomer, the amount of the elastomer added may be 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, relative to 100 parts by mass of the total of the curable components and the elastomer in the curable composition, or 80 parts by mass or less, 50 parts by mass or less, or 30 parts by mass or less.

[0086] The 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 the polymerization initiator include azo-based polymerization initiators and organic peroxide-based polymerization initiators. Examples of azo-based 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-carbonitrile), and dimethyl 1,1'-azobis(1-cyclohexanecarboxylate). , 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), 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 4-cyanopentanoate), and the like. Examples of organic peroxide polymerization initiators include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, α,α'-di(t-butylperoxy)diisopropylbenzene, and tert-butyl hydroperoxide.

[0087] When the curable composition contains a polymerization initiator, the amount of the polymerization initiator added may be in the range of 0.01 to 5 parts by mass per 100 parts by mass of the total of the curable components and elastomer in the curable composition.

[0088] Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, metal hydroxides, etc. When the curable composition contains a flame retardant, the amount of the flame retardant added varies depending on the type of flame retardant, etc., but may be in the range of 0.01 to 50 parts by mass per 100 parts by mass of the total of the curable components and elastomer in the curable composition.

[0089] Examples of coupling agents include silane coupling agents such as γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, 3-(meth)acryloyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. When the curable composition contains a coupling agent, the amount of the coupling agent added may be in the range of 0.1 to 5 parts by mass per 100 parts by mass of the total solid content in the curable composition. Note that the solid content in the curable composition refers to components other than the organic solvent.

[0090] The filler may be either organic or inorganic, but inorganic fillers are preferred. Examples of inorganic fillers include silica (SiO), alumina (AlO), titanium oxide, barium titanate, strontium titanate, potassium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, aluminum borate, silicon carbide, mica, beryllia, clay, and talc. Silica is preferred from the viewpoint of dielectric properties.

[0091] The shape and size of the filler are not particularly limited. The average particle size of the filler may be, for example, 0.01 to 20 μm, or 0.1 to 10 μm. Here, the average particle size of the filler is the particle size at a point corresponding to an integrated value of 50% in a volume-based particle distribution determined by a laser diffraction scattering method.

[0092] When the curable composition 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 of the curable components and elastomer in the curable composition.

[0093] The curable composition may be solvent-free or may contain a solvent. The solvent can adjust the viscosity of the curable composition to further improve the coatability. The solvent is preferably an organic solvent.

[0094] 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.

[0095] When the curable composition contains a solvent, the solid content of the curable composition may be, for example, in the range of 30 to 95 mass %.

[0096] The method for producing the curable composition is not particularly limited. One example of the method for producing the curable composition is a method in which compound (A), compound (B), and optional components used as needed are added and mixed. More specifically, for example, compound (A), compound (B), and optional components used as needed are dissolved or dispersed in a solvent and mixed to obtain the curable composition. The conditions for mixing each component, such as the order, temperature, and time, are not particularly limited and may be appropriately adjusted depending on the type of raw material, production scale, production equipment, etc.

[0097] [Prepreg] According to one embodiment, a prepreg including a curable composition or a semi-cured product of the curable composition can be provided. This prepreg can be formed, for example, using the curable composition and a fibrous substrate. The curable composition can be any of the curable compositions described above. Details of the curable composition are as described above.

[0098] The prepreg includes the curable composition described above or a semi-cured product of the curable composition described above. Regarding the semi-cured product, in the present disclosure, the B-stage state according to JIS K 6800 (1985) can be cited as one indicator of the semi-cured product. The prepreg may, for example, contain the curable composition or a semi-cured product of the curable composition and a fibrous substrate such as a sheet-like fibrous substrate. In the prepreg, the curable composition may be in an uncured state, or the curable composition may be partially or entirely semi-cured.

[0099] A prepreg can be obtained, for example, by coating a fibrous substrate with a curable composition and drying it. For example, a prepreg can be obtained by impregnating a fibrous substrate with the curable composition and then drying the fibrous substrate impregnated with the curable composition. Drying is preferably carried out at a temperature at which volatile components such as solvents contained in the curable composition are removed or higher, and may be carried out at a temperature at which the thermosetting resin contained in the curable composition is semi-cured or higher depending on the application. Furthermore, drying is preferably adjusted so that the thermosetting resin contained in the curable composition is not completely cured. From this perspective, 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 equipment, and its scale.

[0100] The fiber substrate may be any of woven fabric, knitted fabric, and nonwoven fabric. The fiber substrate may be provided in the form of chopped strand mat, roving, etc. The fiber material may be either inorganic fiber or organic fiber. Examples of inorganic fibers include glass fiber and carbon fiber. Examples of glass fibers include E glass, NE glass, D glass, S glass, Q glass, etc. Examples of organic fibers include polyimide, polyester, tetrafluoroethylene, etc. The fiber substrate may be made of one type of these fibers alone or a combination of two or more types of these fibers. From the viewpoints of dielectric properties and heat resistance, the material of the fiber substrate is preferably inorganic fiber, and more preferably glass fiber.

[0101] The fiber substrate may be appropriately selected depending on the application of the prepreg, but a sheet-like fiber substrate is preferred. Examples of the sheet-like fiber substrate include various sheet-like fiber substrates used in known laminates for electrical insulating materials. The thickness of the sheet-like fiber substrate is not particularly limited, but is preferably 0.01 to 0.1 mm, for example. Here, the thickness is measured at five points at equal distances across the entire surface of the sheet-like fiber substrate, and the arithmetic average value of the five measurements is used.

[0102] [Metal-clad laminate] According to one embodiment, a metal-clad laminate can be provided, which includes a cured prepreg and a metal foil. The details of the curable composition and the prepreg are as described above. In the present disclosure, one indicator of the cured product is the C-stage state according to JIS K 6800 (1985).

[0103] The metal-clad laminate preferably includes a prepreg layer and a metal foil disposed on at least one surface of the prepreg layer. The prepreg layer is a cured product of the prepreg described above. For example, in the metal-clad laminate, a metal foil is disposed on at least one surface of the cured prepreg, and more preferably, a metal foil is disposed on both surfaces of the cured prepreg. The metal-clad laminate may be manufactured by disposing a metal foil on at least one surface of a single sheet-like prepreg, or may be manufactured by laminating two or more sheet-like prepregs and disposing a metal foil on at least one surface of the outermost surface of the laminate. For example, the metal-clad laminate may be manufactured by laminating two or more sheet-like prepregs and disposing a metal foil on both surfaces of the laminate.

[0104] As a specific example of a method for producing a metal-clad laminate, a method in which a metal foil is arranged on a laminate of two or more sheet-like prepregs will be described below.

[0105] 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 to each other, 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 composition according to one embodiment.

[0106] Next, a metal foil is placed on at least one surface of this laminate. The laminate with the metal foil placed thereon is heated and pressurized. This promotes the curing reaction of the sheet-like prepreg, resulting in a cured prepreg. Furthermore, adjacent sheet-like prepregs can be bonded together. The heating and pressurizing conditions are not particularly limited, but may be, for example, a temperature of 100 to 300°C, a time of 10 to 300 minutes, and a pressure of 0.5 to 50 MPa. After heating and pressurizing, reheating may be performed to further promote the curing of the prepreg. In this case, the reheating temperature may be 100 to 300°C. As a pressurizing method, for example, an autoclave molding machine, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or the like can be used.

[0107] The metal for the metal foil is not particularly limited, and examples thereof include copper, nickel, aluminum, gold, silver, platinum, molybdenum, ruthenium, tungsten, iron, titanium, chromium, and alloys containing two or more of these metal elements. Industrially, the metals copper, nickel, and aluminum are preferred. By using copper as the metal foil, a copper-clad laminate can be provided.

[0108] [Printed wiring board] According to one embodiment, a printed wiring board including a cured product of a prepreg can be provided. The printed wiring board can be manufactured using 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 the metal-clad laminate are as described above. The printed wiring board may be either a single-layer printed wiring board or a multilayer printed wiring board.

[0109] [Semiconductor Package] According to one embodiment, a semiconductor package can be provided that includes a printed wiring board and a semiconductor element. More specifically, for example, a semiconductor package can be provided that includes a printed wiring board that includes a cured product of a prepreg and a semiconductor element. The semiconductor package can be manufactured, for example, by mounting a semiconductor element, a memory, etc. on a printed wiring board by a known method.

[0110] Examples of embodiments are given below: The present invention is not limited to the following embodiments. <1> A curable composition comprising a compound (A) having a vinylbenzyl group and a compound (B) having a 2,2,6,6-tetramethylpiperidine structure.

[0111] <2> The compound (B) having a 2,2,6,6-tetramethylpiperidine structure is a compound having two or more 2,2,6,6-tetramethylpiperidine structures in one molecule. <1> The curable composition according to claim 1.

[0112] <3> The compound (B) having a 2,2,6,6-tetramethylpiperidine structure is a compound represented by the following general formula (1): <2> The curable composition according to claim 1.

[0113] [ka]

[0114] [In general formula (1), R 1 represents an organic group, and n is an integer of 2 or more.

[0115] <4> The aforementioned <1> ~ <3> A prepreg comprising the curable composition or a semi-cured product of the curable composition according to any one of the above items.

[0116] <5> The aforementioned <4> A metal-clad laminate comprising a cured product of the prepreg according to claim 1 and a metal foil.

[0117] <6> The aforementioned <4> A printed wiring board comprising a cured product of the prepreg according to claim 1.

[0118] <7> The aforementioned <6> A semiconductor package comprising the printed wiring board according to claim 1 and a semiconductor element. [Example]

[0119] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0120] 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 by gel permeation chromatography (GPC) using a calibration curve prepared using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene (TSK standard POLYSTYRENE (Types: A-2500, A-5000, F-20, F-80) manufactured by Tosoh Corporation). The GPC conditions are shown below.

[0121] Apparatus: High-speed GPC apparatus "HLC-8320GPC" (Tosoh Corporation, product name) Detector: Ultraviolet absorption detector "UV-8320" (Tosoh Corporation, product name) Columns: Guard column: TSKgel guard column Super(HZ)-M+, columns: TSKgel SuperMultipore HZ-M (2 columns), reference column: TSKgel SuperH-RC (2 columns) (all products of Tosoh Corporation) Column dimensions: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: tetrahydrofuran Sample concentration: 10mg / 1mL Injection volume: 1μL Flow rate: 0.35mL / min Measurement temperature: 40℃

[0122] 1H-NMR measurement conditions Equipment: JEOL RESONANCE "ECX400II" Solvent: CDCl3 Reference material: tetramethylsilane

[0123] Production Example 1: Production of Compound (A-1) Having a Vinylbenzyl Group A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet was charged with 35.6 parts by mass of indene, 68.7 parts by mass of chloromethylstyrene (*1), 29.0 parts by mass of α-chloro-p-xylene, 7.1 parts by mass of tetra-n-butylammonium bromide (manufactured by Kanto Chemical Co., Inc.) as a phase transfer catalyst, 0.1 parts by mass of phenothiazine as a polymerization inhibitor, and 75.7 parts by mass of toluene as a solvent, and the mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 50 ml / min.

[0124] (*1) Chloromethylstyrene "CMS-P": AGC Seimi Chemical Co., Ltd., a mixture of m- and p-isomers, with m- and p-isomer content of approximately 50% by mass and approximately 50% by mass, respectively.

[0125] Next, 97.0 parts by mass of a 48% by mass aqueous solution of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 20 minutes as a basic compound. The mixture was then stirred at 60°C for 9 hours. Nitrogen was continuously blown in during the reaction. The reaction mixture was cooled to room temperature (25°C), neutralized with a 10% aqueous solution of hydrochloric acid, and then washed twice with pure water. The toluene was distilled off under reduced pressure, and the resulting viscous liquid was washed with methanol and dried in vacuo to obtain a compound (A-1) having a vinylbenzyl group (hereinafter sometimes referred to as "compound (A-1)").

[0126] Compound (A-1) 1H-NMR and GPC analyses confirmed that compound (A-1) contained compounds with one substituent selected from the group consisting of vinylbenzyl and methylbenzyl groups (monosubstituted compounds), two substituents (disubstituted compounds), and three substituents (trisubstituted compounds). The intensity ratio of the compounds in the GPC chart was 9.6:40.1:50.3 for the monosubstituted compounds, disubstituted compounds, and trisubstituted compounds.

[0127] Example 1 and Comparative Example 1: Preparation and evaluation of curable compositions The components were blended according to the blending amounts shown in Table 1, and the blended components were stirred and mixed at 25°C to prepare a curable composition with a solids concentration of approximately 66% by mass. The solids concentration was adjusted by adding toluene. When the blending amounts in Table 1 are for a solution of a component, the amounts refer to the mass converted into solids. The obtained curable composition was subjected to various evaluation tests according to the following procedures, and the results are shown in Table 1.

[0128] Details of each component listed in Table 1 are as follows. Compound (B-1): "BisTEMPO Sebacic Acid" manufactured by Seiko Chemical Co., Ltd., bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate Compound (C-1): "SA9000" manufactured by SABIC, a polyphenylene ether resin having a methacryloyl group at the end, number average molecular weight (Mn) 1700 Polymerization initiator: Fujifilm Wako Pure Chemical Industries, Ltd. "VR-110", 2,2'-azobis(2,4,4-trimethylpentane) Flame retardant: UFC "Mosaflam 585", phosphaphenanthrene flame retardant Coupling agent (1): Shin-Etsu Chemical Co., Ltd. "KBM-503", 3-methacryloxypropyltrimethoxysilane Coupling agent (2): Shin-Etsu Chemical Co., Ltd. "KBM-1003", vinyltrimethoxysilane Silica (1): "HS200" manufactured by AGC Si-Tech Co., Ltd. Silica (2): "NQL2015V" manufactured by Jiangsu NOVORAY New Materials Co., Ltd.

[0129] Prepreg manufacturing A 40 μm thick glass cloth (manufactured by Asahi Kasei Corporation) was impregnated with the curable composition and dried by heating at 130° C. for 10 minutes to obtain a prepreg. The content of solids derived from the curable composition in the prepreg was approximately 80 mass %.

[0130] Measurement of minimum melt viscosity The curable composition portion alone was pulverized into powder and removed from the prepreg obtained above, and molded into tablets with a thickness of approximately 1.2 mm and a diameter of 20 mm, which were used as samples for measuring melt viscosity. The melt viscosity of these samples for measuring melt viscosity was measured under the following conditions, and the minimum melt viscosity value was obtained. Measuring equipment (rheometer): TA Instruments Japan Co., Ltd. "DHR-20" Temperature range and temperature rise conditions: 40 to 150°C, 3°C / min

[0131] Manufacturing of double-sided copper-clad laminates An 18 μm thick electrolytic copper foil ("SI-VSP-AM-3R" (trade name) manufactured by Mitsui Mining & Smelting Co., Ltd.) was laminated on both sides of the prepreg obtained above, with the matte side facing the prepreg. This was heated and pressed at 230°C for 80 minutes under vacuum pressing conditions of 2.0 MPa to obtain a double-sided copper-clad laminate.

[0132] Evaluation of the uniformity of the cured product The cross sections of the copper-clad laminates obtained above were observed with a field emission scanning electron microscope (FE-SEM) (JEOL "JSM-7800F"). A cross-sectional photograph of Example 1 is shown in Figure 1, and a cross-sectional photograph of Comparative Example 1 is shown in Figure 2.

[0133] Copper foil peel strength measurement Using a copper etchant (*2), multiple test pieces were prepared by removing the copper foil from the double-sided copper-clad laminate obtained above, leaving only a 3 mm wide strip. Using a tensile tester (Shimadzu Corporation's "EZ Test"), the strip was peeled off in a 90° direction at a speed of 50 mm / min, and the copper foil peel strength was measured.

[0134] (*2) Copper etching solution: 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Inc.)

[0135] Evaluation of solder heat resistance The double-sided copper-clad laminate obtained above was cut into 30mm square pieces to serve as test pieces. The test pieces were floated in a solder bath at 288°C, and the appearance was observed to measure the time until blistering occurred. The test was carried out for a maximum of 1200 seconds, and if no blistering was observed by the time 1200 seconds had elapsed, it was evaluated as ">1200".

[0136] [Table 1]

[0137] The curable composition of Example 1 containing Compound (A) and Compound (B) was able to give a highly homogeneous cured product, as shown in Figure 1. Furthermore, as shown in Table 1, the progress of the polymerization reaction was controlled in the curable composition of Example 1, and the minimum melt viscosity was kept low, which improved the impregnation of glass cloth. As a result, the composition was able to have excellent peel strength and solder heat resistance when used in a double-sided copper-clad laminate.

Claims

1. A curable composition comprising a compound (A) having a vinylbenzyl group and a compound (B) having a 2,2,6,6-tetramethylpiperidine structure.

2. 2. The curable composition according to claim 1, wherein the compound (B) having a 2,2,6,6-tetramethylpiperidine structure is a compound having two or more 2,2,6,6-tetramethylpiperidine structures in one molecule.

3. The curable composition according to claim 2, wherein the compound (B) having a 2,2,6,6-tetramethylpiperidine structure is a compound represented by the following general formula (1): 【Chemical 1】 [In general formula (1), R １ represents an organic group, and n is an integer of 2 or more.

4. A prepreg comprising the curable composition or a semi-cured product of the curable composition according to any one of claims 1 to 3.

5. A metal-clad laminate comprising the cured prepreg according to claim 4 and a metal foil.

6. A printed wiring board comprising a cured product of the prepreg according to claim 4.

7. A semiconductor package comprising the printed wiring board according to claim 6 and a semiconductor element.

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