Resin composition, cured product, sheet-like laminate material, resin sheet, printed wiring board, and semiconductor device

Abstract

Provided is a resin composition with which it is possible to obtain a cured product wherein the dielectric loss tangent can be kept low and increases in the melt viscosity can be suppressed. This resin composition contains (A) a silane compound represented by formula (A-1), (B) an epoxy resin, and (C) an active ester compound. Formula (A-1): (RO)nSiAr4-n (In the formula, R represents an alkyl group, Ar represents an aryl group, and n represents 1 or 2.)

Description

[Technical field]

[0001] The present invention relates to a resin composition containing an epoxy resin, and further to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method using the build-up method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for further improvement in the dielectric properties, such as the dielectric loss tangent, of the insulating layer.

[0003] It has been known that the dielectric tangent of an insulating layer can be reduced by using an epoxy resin composition containing an active ester compound instead of a typical phenol-based curing agent as a resin composition for forming an insulating layer (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-23714 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when an active ester compound is used, the melt viscosity of the resulting cured product (insulating layer) tends to be high.

[0006] An object of the present invention is to provide a resin composition which can give a cured product having a low dielectric tangent and which can suppress an increase in melt viscosity. [Means for solving the problem]

[0007] Means for Solving the Problems of the Invention The present inventors conducted intensive research and, as a result, unexpectedly found that by using an epoxy resin and an active ester compound as components of a resin composition, and further containing a silane compound having a specific structure, it is possible to obtain a cured product that can suppress the dielectric tangent to be low and the increase in melt viscosity, and thus completed the present invention.

[0008] That is, the present invention includes the following. [1] A resin composition comprising (A) a silane compound represented by the following formula (A-1), (B) an epoxy resin, and (C) an active ester compound: (RO) n SiAr 4-n (A-1) (In the formula, R represents an alkyl group, Ar represents an aryl group, and n represents 1 or 2.) [2] The resin composition according to the above-mentioned [1], wherein the content of the component (A) is 0.05% by mass or more and 1% by mass or less, when the resin component in the resin composition is taken as 100% by mass. [3] The resin composition according to the above [1] or [2], further comprising (D) an inorganic filler. [4] The resin composition according to the above item [3], wherein the (D) inorganic filler is surface-treated with a surface treatment agent, and the surface treatment agent is an alkoxysilane compound different from the (A) component. [5] The resin composition according to the above [4], wherein the alkoxysilane compound different from the component (A) contains an amino-silane coupling agent. [6] The resin composition according to any one of the above [1] to [5], further comprising (E) a radically polymerizable compound. [7] The resin composition according to the above [6], wherein the radically polymerizable compound (E) contains a maleimide compound (E1). [8] The resin composition according to the above item [7], wherein the maleimide compound (E1) comprises at least one selected from the group consisting of (E1-1a) maleimide compounds having a trimethylindane skeleton, and (E1-2) maleimide resins having an aromatic ring skeleton directly bonded to a nitrogen atom of the maleimide group. [9] The resin composition according to any one of the above [1] to [8], which is for forming an interlayer insulating layer of a printed wiring board.

[10] A cured product of the resin composition according to any one of the above items [1] to [9].

[11] A sheet-like laminate material comprising the resin composition according to any one of the above items [1] to [9].

[12] A resin sheet comprising: a support; and a resin composition layer formed on the support, the resin composition being formed from the resin composition according to any one of the above items [1] to [9].

[13] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of the above [1] to [9].

[14] A semiconductor device comprising the printed wiring board according to

[13] above. Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product that can suppress the dielectric tangent to be low and the increase in melt viscosity; a cured product of the resin composition; a sheet-like laminate material and a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device containing the cured product of the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be modified and implemented as desired without departing from the scope of the claims of the present invention and the scope of equivalents thereof.

[0011] In the following description, the amount of each component is the amount of non-volatile component, unless otherwise specified. In the following description, the "non-volatile components in the resin composition" may include (D) inorganic filler unless otherwise specified. In addition, in the following description, the "resin components" refers to the non-volatile components contained in the resin composition excluding (D) inorganic filler unless otherwise specified, and here, (D) inorganic filler may be a surface-treated inorganic filler as described below.

[0012] <Resin composition> The resin composition of the present invention includes (A) a silane compound represented by formula (A-1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product that can achieve both a low dielectric tangent and a low melt viscosity can be obtained. In addition, in the present invention, it is usually possible to obtain a cured product having a low average coefficient of thermal expansion (CTE) and a low relative dielectric constant.

[0013] The resin composition of the present invention may further contain optional components in addition to the silane compound represented by formula (A-1), the epoxy resin (B), and the active ester compound (C). Examples of the optional components include an inorganic filler (D), a radical polymerizable compound (E), other curing agents (F), a curing accelerator (G), other additives (H), and an organic solvent (K). In this specification, each of the above components (A) to (K) may also be referred to as "component (A)", "component (B)", etc. Each component contained in the resin composition will be described in detail below.

[0014] <(A) Silane compound represented by formula (A-1)> The silane compound used in the present invention is not particularly limited as long as it is a compound represented by the following formula (A-1): In this specification, the component (A) may be simply referred to as the "specific silane compound". (RO) n SiAr 4-n (A-1) (In the formula, R represents an alkyl group, Ar represents an aryl group, and n represents 1 or 2.)

[0015] The alkyl group represented by R is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably one or more selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.

[0016] The aryl group represented by Ar is preferably an aryl group having 6 to 10 carbon atoms, and may be an aryl group having a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is even more preferable, and one or more selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group is even more preferable, and a methyl group is particularly preferable. The aryl group represented by Ar is preferably at least one selected from the group consisting of a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, more preferably at least one selected from the group consisting of a phenyl group, a tolyl group, and a xylyl group, and even more preferably a phenyl group.

[0017] The number n is preferably 2.

[0018] Specific examples of the specific silane compound include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenylmethoxyethoxysilane, diphenylmethoxypropoxysilane, diphenylethoxypropoxysilane, and other diphenyldialkoxysilanes; triphenylmethoxysilane, triphenylethoxysilane, triphenylpropoxysilane, and other triphenylalkoxysilanes; and the like. Diphenyldialkoxysilanes are preferred, and diphenyldimethoxysilane is more preferred.

[0019] When the resin composition contains a specific silane compound, the dispersibility of the particles and components contained in the resin composition is improved, and the increase in the melt viscosity of the cured product obtained from the resin composition can be suppressed. In particular, when the resin composition contains an inorganic filler (D), the melt viscosity of the cured product obtained from the resin composition tends to increase, but by including the specific silane compound, the dispersibility of the inorganic filler (particles) (D) is improved, and the increase in the melt viscosity of the cured product obtained from the resin composition can be effectively suppressed. The specific silane compound may be used alone or in combination of two or more kinds in any ratio.

[0020] The content of component (A) is, relative to 100 mass% of the nonvolatile components in the resin composition, for example, 0.01 mass% or more, preferably 0.05 mass% or more, and for example, 1 mass% or less, preferably 0.8 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.3 mass% or less, and even more preferably 0.2 mass% or less.

[0021] The content of the (A) component, relative to 100 mass% of the resin components in the resin composition, is, for example, 0.05 mass% or more, 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.3 to 0.30 mass% or more, even more preferably 0.32 mass% or more, and for example, 1 mass% or less, preferably 0.8 mass% or less, more preferably 0.6 mass% or less, even more preferably 0.5 to 0.50 mass% or less, and even more preferably 0.45 mass% or less.

[0022] <(B) Epoxy resin> The resin composition of the present invention contains an epoxy resin (B). The epoxy resin (B) means a curable resin having an epoxy group.

[0023] (B) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, and the like. Examples of the epoxy resins include cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, phenolphthalimidine type epoxy resins, phenolphthalein type epoxy resins, etc. (B) The epoxy resins may be used alone or in combination of two or more.

[0024] The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile components of the (B) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0025] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resins as epoxy resins, or may contain only solid epoxy resins, or may contain a combination of liquid epoxy resins and solid epoxy resins. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

[0026] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0027] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0028] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3 980S" (glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel & Sumitomo Metal Chemical's "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (epoxy resin having a butadiene structure); Nippon Steel & Sumitomo Metal Chemical's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used alone or in combination of two or more.

[0029] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0030] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, and phenolphthalein type epoxy resins.

[0031] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-73" manufactured by DIC Corporation. 11", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V" manufactured by Nippon Steel Chemical & Material Co., Ltd. (Naphthalene type epoxy resin); "ESN485" (Naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (Dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (Biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (Anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX77" manufactured by Mitsubishi Chemical Co., Ltd. Examples of epoxy resins include "PG-100" (phenol aralkyl type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical, "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical, and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more types.

[0032] When a liquid epoxy resin and a solid epoxy resin are used in combination as the (B) epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin / solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

[0033] The epoxy equivalent of the (B) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0034] The weight average molecular weight (Mw) of the epoxy resin (B) is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0035] The content of the (B) component, relative to 100 mass% of the non-volatile components in the resin composition, is, for example, 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, even more preferably 7.5 mass% or more, and for example, 30 mass% or less, preferably 20 mass% or less, more preferably 18 mass% or less, even more preferably 15 mass% or less, and even more preferably 12 to 12.0 mass% or less.

[0036] The content of the (B) component, relative to 100 mass% of the resin components in the resin composition, is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, even more preferably 30 mass% or more, particularly preferably 32 to 32.0 mass% or more, and is, for example, 60 mass% or less, preferably 55 mass% or less, more preferably 50 mass% or less, even more preferably 45 mass% or less, even more preferably 40 mass% or less, and particularly preferably 35 mass% or less.

[0037] <(C) Active ester compound> The resin composition of the present invention contains an active ester compound (C). The active ester compound (C) may be used alone or in combination of two or more at any ratio. The active ester compound (C) may have a function of reacting with the epoxy resin (B) to crosslink the epoxy resin (B). The active ester compound (C) may have a carbon-carbon unsaturated bond.

[0038] As the (C) active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester compound is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0039] Specifically, the (C) active ester compound is preferably a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, or an active ester compound containing a benzoylated product of phenol novolac, and more preferably at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound, and even more preferably a dicyclopentadiene type active ester compound. The dicyclopentadiene type active ester compound is preferably an active ester compound containing a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0040] (C) Commercially available active ester compounds include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", and "EXB-8150-62T" ", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation); an active ester compound containing phosphorus, "EXB9401" (manufactured by DIC Corporation); an active ester compound which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds which are benzoylated products of phenol novolac, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0041] The active ester group equivalent of the (C) active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0042] The ratio of the amounts of the (B) component and the (C) component is preferably 1.0 or more, more preferably 1.01 or more, even more preferably 1.05 or more, even more preferably 1.1 to 1.10 or more, particularly preferably 1.11 or more, and is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.4 or less, and even more preferably 1.3 or less, when the ratio of the (B) component and the (C) component is within the above range, the effects of the present invention can be easily obtained.

[0043] The content of component (C) is, relative to 100 mass% of nonvolatile components in the resin composition, for example, 3 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more, even more preferably 13 mass% or more, and for example, 40 mass% or less, preferably 35 mass% or less, more preferably 30 mass% or less, even more preferably 25 mass% or less, and even more preferably 21 mass% or less.

[0044] The content of the (C) component, relative to 100 mass% of the resin components in the resin composition, is, for example, 30 mass% or more, preferably 40 mass% or more, more preferably 45 mass% or more, even more preferably 50 mass% or more, even more preferably 55 mass% or more, and particularly preferably 57 mass% or more, and is, for example, 80 mass% or less, preferably 75 mass% or less, more preferably 70 mass% or less, even more preferably 65 mass% or less, and even more preferably 60 mass% or less.

[0045] <(D) Inorganic filler> The resin composition of the present invention may contain an inorganic filler (D) as an optional component. The inorganic filler (D) is contained in the resin composition in the form of particles. The inorganic filler (D) may be used alone or in any combination of two or more kinds.

[0046] (D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica. The (D) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0047] (D) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", "YA010C", and "180nmSX-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellfiers" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Sferique", "BA-1", and "BA-S" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0048] The average particle size of the (D) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (D) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the (D) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0049] The specific surface area of ​​the (D) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0050] It is preferable that the inorganic filler (D) is surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the inorganic filler (D) can be improved. As the surface treatment agent, an alkoxysilane compound different from the component (A) is preferable, for example, a vinyl-based silane coupling agent such as vinyltrimethoxysilane or vinyltriethoxysilane; an epoxy-based silane coupling agent such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, or 3-glycidoxypropyltriethoxysilane; p- Styryl-based silane coupling agents such as styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, amino-based silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris-(trimethoxysilylpropyl)isopropylamine; Isocyanurate-based silane coupling agents such as socyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents;Examples of the non-silane coupling alkoxysilane compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. The surface treatment agent may be used alone or in combination of two or more in any ratio.

[0051] Commercially available surface treatment agents include, for example, "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", and "KBE-403" (epoxy-based silane coupling agents); "KBM-1403" (styryl-based silane coupling agents); "KBM-502", "KBM-503", "KBE-502", and "KBE-503" (methacrylic-based silane coupling agents); "KBM-5103" (acrylic-based silane coupling agents); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", and "KBM-575" (amino-based silane coupling agents); Examples include "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", and "KBM-7103" (non-silane coupling alkoxysilane compound).

[0052] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100 mass% of the inorganic filler is preferably surface-treated with 0.2 mass% to 5 mass% of the surface treatment agent, more preferably 0.2 mass% to 3 mass%, and even more preferably 0.3 mass% to 2 mass%.

[0053] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0054] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0055] The content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be preferably 90 mass% or less, more preferably 85 mass% or less, even more preferably 80 mass% or less, and even more preferably 76 mass% or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be, for example, 0 mass% or more, 1 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, etc., preferably 40 mass% or more, more preferably 50 mass% or more, even more preferably 55 mass% or more, even more preferably 60 mass% or more, and particularly preferably 61 mass% or more.

[0056] <(E) Radical Polymerizable Compound> The resin composition of the present invention may contain a radically polymerizable compound (E) as an optional component. The radically polymerizable compound (E) may be used alone or in any combination of two or more kinds.

[0057] The type of the radical polymerizable compound is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable compound include compounds having one or more radical polymerizable unsaturated groups selected from maleimide group, vinyl group, allyl group, styryl group, vinylphenyl group, acryloyl group, methacryloyl group, fumaroyl group, and maleoyl group. Among them, from the viewpoint of easily obtaining a cured product with excellent dielectric properties, it is preferable to contain (E1) a maleimide compound and / or (E2) other radical polymerizable compounds. (E2) Other radical polymerizable compounds are compounds that do not have a maleimide group and have a radical polymerizable unsaturated group other than a maleimide group, and among them, it is preferable to contain one or more selected from (meth)acrylic resins and styryl resins.

[0058] (E1) The maleimide compound is not particularly limited in type, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of the maleimide compound include maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from dimer diamine), such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all manufactured by Designer Molecules), and "SLK-2700" (manufactured by Shin-Etsu Chemical Co., Ltd.). (E1-1) Maleimide resins containing an indane skeleton, as described in the Japan Institute of Invention and Innovation Disclosure Technical Journal No. 2020-500211; "MIR- Preferred are maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group (E1-2), such as "MIR-3000-70MT," "MIR-5000-60T" (both manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.), and as the latter (E1-2) maleimide resin, a bismaleimide resin containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group (E1-2a) and containing three or more aromatic rings in the molecule, such as "MIR-5000-60T" (manufactured by Nippon Kayaku Co., Ltd.), is more preferred.

[0059] As the (E1) maleimide compound, it is preferable to include a maleimide compound containing an indane skeleton (also referred to as "(E1-1) specific maleimide compound" in this specification), and it is more preferable to include a maleimide compound containing a trimethylindane skeleton (E1-1a). The (E1-1) specific maleimide compound can be produced, for example, by the method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211. According to the production method described in this Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method includes a structure represented by the following formula (M1). Therefore, the (E1) maleimide compound may include a maleimide compound including a structure represented by formula (M1).

[0060] [ka]

[0061] (In formula (M1), R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n1 represents the average number of repeating units of 0.95 to 10.0; each independently represents an integer of 0 to 4; and each independently represents an integer of 0 to 3. R 1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. 2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. 1 may be the same or different in the same ring. When n3 is 2 to 3, R 2 may be the same or different in the same ring.

[0062] In formula (M1), n1 represents the average number of repeating units, and its range is 0.95 to 10.0. According to the manufacturing method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211, a group of maleimide compounds containing a structure represented by formula (M1) can be obtained. As can be seen from the fact that the average number of repeating units n1 in formula (M1) can be smaller than 1.00, the maleimide compound containing the structure represented by formula (M1) thus obtained can contain a maleimide compound having a trimethylindane skeleton repeating unit number of 0. Therefore, the maleimide compound containing the structure represented by formula (M1) can be purified to obtain a specific maleimide compound (E1-1) excluding the maleimide compound having a trimethylindane skeleton repeating unit number of 0, and the resin composition may contain only the specific maleimide compound (E1-1) obtained. However, even if the maleimide compound having a trimethylindane skeleton repeating unit number of 0 is contained in the resin composition, the effect of the present invention can be obtained. In addition, when purification is omitted, it is possible to suppress costs. Therefore, it is preferable that the resin composition contains a maleimide compound containing a structure represented by formula (M1), without excluding any maleimide compound having a trimethylindane skeleton with zero repeating units.

[0063] In formula (M1), the average number of repeating units n1 is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, particularly preferably 1.1 or more, and is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, particularly preferably 6.0 or less. When the average number of repeating units n1 is within the above range, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

[0064] Examples of the structure represented by formula (M1) include the following.

[0065] [ka]

[0066] The maleimide compound containing the structure represented by formula (M1) may further contain a structure represented by the following formula (M2): For example, the maleimide compound containing the structure represented by formula (M1) is a compound represented by formula (M1) in which n2 is 3 or less and R is present at two or more of the ortho and para positions relative to the maleimide group of the benzene ring to which the maleimide group is bonded. 1 When is not bonded, the structure represented by formula (M1) may include a structure represented by formula (M2) in combination with the structure represented by formula (M1).

[0067] [ka] (In formula (M2), R c1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R c2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; c1 is the number of repeating units and represents an integer of 1 to 20; n c2 each independently represents an integer of 0 to 4; c3 each independently represents an integer of 0 to 3; * represents a bond. c1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. c2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. c2 If is between 2 and 4, Rc1 may be the same or different in the same ring. c3 If is 2-3, R c2 may be the same or different in the same ring.

[0068] The maleimide compound containing the structure represented by formula (M1) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement in a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is expressed as "Mw / Mn". Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (M1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (M1) is in the above range, the effects of the present invention can be significantly obtained.

[0069] Of the maleimide compounds containing a structure represented by formula (M1), the amount of the maleimide compound having an average repeating unit number n1 of 0 is preferably within a specific range. When the GPC measurement of the maleimide compound containing a structure represented by formula (M1) is performed, the amount of the maleimide compound having an average repeating unit number n1 of 0 can be expressed in area % based on the results of the GPC measurement. In detail, the amount of the maleimide compound having an average repeating unit number n1 of 0 can be expressed by the ratio (area %) of the peak area of ​​the maleimide compound containing a structure represented by formula (M1) to the total area of ​​the peaks of the maleimide compound containing a structure represented by formula (M1). Specifically, the amount of the maleimide compound having an average repeating unit number n1 of 0 is preferably 32 area % or less, more preferably 30 area % or less, and even more preferably 28 area % or less, relative to the total amount of the maleimide compound containing a structure represented by formula (M1) (100 area %). When the amount of the maleimide compound having an average repeating unit number n1 of 0 is within the above range, the effects of the present invention can be significantly obtained.

[0070] The maleimide group equivalent of the maleimide compound containing the structure represented by formula (M1) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, particularly preferably 200 g / eq. or more, and preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, particularly preferably 800 g / eq. or less. The maleimide group equivalent represents the mass of the maleimide compound per equivalent of maleimide group. When the maleimide group equivalent of the maleimide compound containing the structure represented by formula (M1) is within the above range, the effects of the present invention can be significantly obtained.

[0071] Among the (E2) other radically polymerizable compounds, the (meth)acrylic resin is not particularly limited in type as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and may be a monomer or an oligomer. Here, the term "(meth)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. Examples of the methacrylic resin include (meth)acrylate monomers, as well as (meth)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0072] The type of styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and it may be a monomer or an oligomer. Examples of styryl resins include styryl resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.). Examples of styryl resins include styrene monomers, as well as homopolymers of aromatic divinyl compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether, or copolymers of these aromatic divinyl compounds with aromatic monovinyl compounds such as styrene, vinyltoluene, ethylstyrene, and vinylnaphthalene.

[0073] The content of the (E) radically polymerizable compound in the resin composition may be 0% by mass or more than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, and is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2 to 2.0% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0074] The content of the (E) radically polymerizable compound in the resin composition may be 0% by mass or more than 0% by mass, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, still more preferably 2% by mass or more, particularly preferably 2.5% by mass or more, and is, for example, 20% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3.5% by mass or less.

[0075] <(F) Other hardeners> The resin composition of the present invention may contain (F) other curing agents as optional components. The (F) other curing agents do not include those corresponding to the above-mentioned (A) to (C) and (E) components. The (F) other curing agents, like the above-mentioned (C) active ester compound, can function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure the resin composition. The (F) other curing agents may be used alone or in combination of two or more.

[0076] (F) Examples of other curing agents include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. Among these, it is preferable to use one or more curing agents selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.

[0077] As the phenol-based curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. From the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac resin is preferred. Specific examples of phenol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

[0078] As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more, carbodiimide structures in one molecule can be used. Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly( Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P", "Stavaxol P400", and "Hi-Kasil 510" manufactured by Rhein Chemie.

[0079] As the acid anhydride curing agent, a curing agent having one or more acid anhydride groups in one molecule can be used, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Clay Valley.

[0080] As the amine-based curing agent, a curing agent having one or more, preferably two or more, amino groups in one molecule can be used. As the amine-based curing agent, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be mentioned, among which aromatic amines are preferred. As the amine-based curing agent, primary amines or secondary amines are preferred, and primary amines are more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0081] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0082] Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both of which are phenol novolac-type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

[0083] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0084] The active group equivalent of the (F) other curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent represents the mass of the curing agent per equivalent of the active group.

[0085] The ratio of the amount of epoxy resin to the curing agent, that is, the ratio of the amount of the (B) component to the (C) component and the (F) component, is preferably 1.0 or more, more preferably 1.01 or more, more preferably 1.1 to 1.10 or more, even more preferably 1.2 to 1.20 or more, particularly preferably 1.25 or more, and is preferably 2.0 or less, more preferably 1.75 or less, more preferably 1.5 or less, even more preferably 1.4 to 1.40 or less, and particularly preferably 1.3 to 1.30 or less, when the ratio of the amount of the epoxy resin to the curing agent is within the above range, the effect of the present invention can be easily obtained.

[0086] The content of (F) other curing agent in the resin composition may be 0% by mass or may be more than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 2% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0087] The content of (F) other curing agent in the resin composition may be 0% by mass or may be more than 0% by mass, and is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, particularly preferably 5.0% by mass or more, and is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 6% by mass or less, when the resin component in the resin composition is 100% by mass.

[0088] <(G) Curing accelerator> The resin composition of the present invention may contain a curing accelerator (G) as an optional component.

[0089] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. The (G) curing accelerator may be used alone or in combination of two or more kinds.

[0090] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate ... aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0091] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0092] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0093] Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0094] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0095] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0096] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0097] As the amine-based curing accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0098] The content of the (G) curing accelerator in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, when the non-volatile components in the resin composition are 100% by mass. The lower limit of the content of the (E) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, when the non-volatile components in the resin composition are 100% by mass.

[0099] <(H) Polymer compound> The resin composition of the present invention may contain a polymer compound as the component (H).

[0100] Examples of the polymer compound include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. The polymer compound may be used alone or in combination of two or more.

[0101] The weight average molecular weight of the polymer compound in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the polymer compound in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the polymer compound in terms of polystyrene is measured at a column temperature of 40°C using a measuring device LC-9A / RID-6A manufactured by Shimadzu Corporation, a column Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK, and chloroform or the like as a mobile phase, and can be calculated using a calibration curve of standard polystyrene.

[0102] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of phenoxy resins include "1256" and "4250" (both of which are phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation. Other examples include "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd., and "YX7553", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0103] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred.Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and S-LEC BH series, BX series, KS series, BL series, and BM series, all of which are manufactured by Sekisui Chemical Co., Ltd.

[0104] The polyimide resin may be a resin having an imide structure (preferably a cyclic imide structure), for example, an imide of a diamine compound and an acid anhydride.

[0105] The diamine compound for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0106] Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and dimer acid diamines (hereinafter also referred to as "dimer diamines"). Dimer diamines are preferred. The dimer acid diamine refers to a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of a dimer acid with an aminomethyl group (-CH2-NH2) or an amino group (-NH2). Dimer acid is a compound obtained by dimerizing an unsaturated fatty acid (preferably one having 11 to 22 carbon atoms, particularly preferably one having 18 carbon atoms), and its industrial production process is also publicly known.

[0107] Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a dianiline compound. The phenylenediamine compound means a compound containing a benzene ring having two amino groups, and examples thereof include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine. The naphthalene diamine compound means a compound containing a naphthalene ring having two amino groups, and examples thereof include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene. The dianiline compound means a compound containing two aniline structures in the molecule, and examples thereof include 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, and the like.

[0108] The diamine compound may be a commercially available product or may be synthesized by a known method. The diamine compound may be used alone or in combination of two or more kinds.

[0109] The acid anhydride for preparing the polyimide resin is not particularly limited, but is preferably a tetracarboxylic acid anhydride, and examples thereof include aromatic tetracarboxylic acid dianhydrides and aliphatic tetracarboxylic acid dianhydrides.

[0110] Examples of aromatic tetracarboxylic dianhydrides include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride, and the like, with diphthalic dianhydride being preferred. Benzenetetracarboxylic dianhydride means a dianhydride derived from a compound containing a benzene ring having four carboxy groups, and examples thereof include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride. Naphthalenetetracarboxylic dianhydride means a dianhydride derived from a compound containing a naphthalene ring having four carboxy groups, and examples thereof include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride. Anthracenetetracarboxylic dianhydride means a dianhydride derived from a compound containing an anthracene ring having four carboxy groups, and examples thereof include 2,3,6,7-anthracenetetracarboxylic dianhydride. Diphthalic dianhydride means a compound containing two phthalic anhydride structures in the molecule, and the two phthalic anhydrides in the diphthalic dianhydride may be bonded to each other by a direct bond or via a divalent linking group having 1 to 100 (preferably 1 to 50, more preferably 1 to 20) skeletal atoms selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of diphthalic dianhydride include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic Acid dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, and the like.

[0111] Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

[0112] The acid anhydride such as tetracarboxylic dianhydride may be a commercially available product, or may be synthesized by a known method or a method similar thereto. The acid anhydride may be used alone or in combination of two or more kinds.

[0113] Other examples of polyimide resins include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of polyimide resins include modified polyimides such as linear polyimides obtained by reacting bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (disclosed in JP-A-2006-37083), and polysiloxane skeleton-containing polyimides (disclosed in JP-A-2002-12667 and JP-A-2000-319386, etc.).

[0114] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as polysiloxane skeleton-containing polyamide-imides "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

[0115] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0116] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0117] When the resin composition of the present invention contains the (E) component, the content of the (E) component in the resin composition may be determined according to the properties required for the resin composition, but when the resin components in the resin composition are taken as 100 mass%, it is, for example, 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, 0.6 mass% or more, 0.8 mass% or more, or 1 mass% or more. The upper limit of the content of the (E) component is not particularly limited, but may be, for example, 20 mass% or less, 18 mass% or less, 16 mass% or less, or 15 mass% or less.

[0118] <(I) Other additives> The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy curing agents other than active ester compounds such as phenol curing agents, naphthol curing agents, acid anhydride curing agents, thiol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, and imidazole curing agents; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; benzoto UV absorbers such as triazole-based UV absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus ), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide), and other flame retardants; dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (F) Other additives may be used alone or in combination of two or more at any ratio. (H) The content of other additives can be appropriately determined by those skilled in the art.

[0119] <(K) Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. As the (K) organic solvent, a known one may be appropriately used, and the type is not particularly limited. As the (K) organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc. Examples of the organic solvent include ether ester solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent (K) may be used alone or in combination of two or more in any ratio.

[0120] In one embodiment, the content of the (K) organic solvent is not particularly limited, but when all components in the resin composition are taken as 100 mass%, it can be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, etc.

[0121] <Method of producing resin composition> The resin composition of the present invention can be produced, for example, by adding and mixing in an arbitrary preparation vessel (A) a silane compound represented by formula (A-1), (B) an epoxy resin, and (C) an active ester compound, if necessary (D) an inorganic filler, if necessary (E) a radically polymerizable compound, if necessary (F) other curing agents, if necessary (G) a curing accelerator, if necessary (H) other additives, if necessary, and if necessary (K) an organic solvent, in any order and / or partially or entirely at the same time. In addition, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0122] <Characteristics of resin composition> The resin composition of the present invention comprises (A) a silane compound represented by formula (A-1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product that can achieve both a low dielectric tangent and a low melt viscosity can be obtained, and preferably, a cured product having a low average coefficient of thermal expansion (CTE) and a low relative dielectric constant can be obtained.

[0123] The cured product of the resin composition of the present invention may have a feature that the increase in melt viscosity can be suppressed. Therefore, in one embodiment, the minimum melt viscosity measured by a dynamic viscoelasticity measuring device at a frequency of 1 Hz, a strain of 5 degrees, a load of 100 g, a heating rate of 5°C / min, and a temperature range of 60°C to 180°C as in the following Test Example 3 may be preferably 4000 poise or less, 3000 poise or less, more preferably 2000 poise or less, 1700 poise or less, even more preferably 1500 poise or less, 1300 poise or less, and particularly preferably 1100 poise or less, and among them, when the resin composition contains an inorganic filler (D) containing hollow silica, it can be further lowered, preferably 2000 poise or less, more preferably 1700 poise or less, even more preferably 1500 poise or less, even more preferably 1300 poise or less, and particularly preferably 1100 poise or less.

[0124] The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition, as measured at 5.8 GHz and 23° C. as in Test Example 1 below, may be preferably 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, even more preferably 0.007 or less, 0.006 or less, even more preferably 0.005 or less, and particularly preferably 0.004 or less.

[0125] The cured product of the resin composition of the present invention may be characterized by a low average coefficient of thermal expansion (CTE). Thus, in one embodiment, the average coefficient of thermal expansion of the cured product of the resin composition from 25°C to 150°C, as measured at a heating rate of 5°C / min on an evaluation sample cut to a length of 20 mm and a width of 6 mm as in Test Example 2 below, may be, for example, 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, even more preferably 28 ppm or less, even more preferably 25 ppm or less, and particularly preferably 23 ppm or less.

[0126] The cured product of the resin composition of the present invention may be characterized by a low relative dielectric constant (Dk). Thus, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition measured at 5.8 GHz and 23°C as in the following Test Example 1 can be preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.5 or less, and even more preferably 3.3 or less, and among them, when the resin composition contains (D) an inorganic filler containing hollow silica, it can be further lowered, for example, 5.0 or less, preferably 4.0 or less, more preferably 3.5 or less, even more preferably 3.3 or less, even more preferably 3.0 or less, and particularly preferably 2.8 or less.

[0127] <Applications of resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer. In addition, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.

[0128] In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0129] Furthermore, the resin composition of the present invention provides an insulating layer with good component embedding properties, and therefore can be suitably used when the printed wiring board is a circuit board with built-in components.

[0130] <Sheet-type laminated material> The resin composition of the present invention can be used by coating in the form of a varnish, but from an industrial perspective, it is generally preferred to use the resin composition in the form of a sheet-like laminate material containing the resin composition.

[0131] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0132] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0133] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0134] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0135] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0136] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0137] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0138] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0139] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0140] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0141] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0142] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0143] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0144] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0145] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0146] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0147] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0148] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0149] The sheet-like laminate material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0150] <Printed wiring board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0151] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0152] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0153] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0154] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0155] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0156] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0157] The support may be removed between step (I) and step (II) or after step (II).

[0158] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0159] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0160] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0161] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0162] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

[0163] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0164] Step (IV) is a step of roughening the insulating layer. Usually, smears are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by carrying out a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0165] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0166] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0167] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0168] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0169] In the step (V), a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used for the conductor layer.

[0170] In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0171] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0172] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0173] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0174] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0175] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out step (V) between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method, using the metal foil on the insulating layer.

[0176] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0177] <Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

[0178] Examples of the semiconductor device include various semiconductor devices used in electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.). EXAMPLES

[0179] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature condition is room temperature (25°C).

[0180] [Example 1] Naphthalene-skeleton epoxy resin (DIC Corporation "HP-4032-SS", epoxy equivalent 144 g / eq.) 15 parts, active ester curing agent (DIC Corporation "HPC-8150-62T", toluene solution with 62% non-volatile content by mass, active ester group equivalent 234 g / eq.) 43 parts, diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-202SS") as component (A) 0.2 parts, aminotriazine-containing cresol novolac resin (DIC Corporation "LA-3018-50P", 1-methoxy-2-propanol solution with 50% non-volatile content by mass) 5 parts, inorganic filler (spherical silica (Admatechs Co., Ltd. "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd. "KBM573") 2 A resin varnish was obtained by mixing 140 parts of a binder (1.0 parts per million / g) and 0.5 parts of a curing catalyst (1B2PZ, manufactured by Shikoku Chemical Industry Co., Ltd.) as a curing accelerator and dispersing the mixture uniformly using a high-speed rotating mixer.

[0181] [Example 2] An MEK solution (62% by mass of non-volatile components) of maleimide compound A (Mw / Mn=1.81, t''=1.47 (mainly 1, 2 or 3)) represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation Disclosure Technical Journal Publication No. 2020-500211 was prepared.

[0182] [ka]

[0183] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler in Example 1 was changed to 145 parts, and 2 parts of a MEK solution of maleimide compound A (non-volatile component 62% by mass) was added as the maleimide compound.

[0184] [Example 3] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler was changed to 145 parts and 2 parts of a maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd., a toluene solution with a non-volatile content of 60% by mass) was added.

[0185] [Example 4] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler was changed to 145 parts and 2 parts of a maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene solution with a non-volatile content of 70% by mass) was added.

[0186] [Example 5] In Example 1, the amount of inorganic filler was changed to 145 parts, Styryl resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Company, Inc., toluene solution with 65% non-volatile content) A resin varnish was obtained in the same manner as in Example 1, except that 2 parts of the ethyl acetate was added.

[0187] [Comparative Example 1] A resin varnish was obtained in the same manner as in Example 1, except that 0.2 parts of the silane compound ("KBM-202SS" manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (A) was not used.

[0188] [Comparative Example 2] A resin varnish was obtained in the same manner as in Example 1, except that 0.2 parts of the silane compound ("KBM-202SS" manufactured by Shin-Etsu Chemical Co., Ltd.) as component (A) was not used, and 0.2 parts of dimethyldimethoxysilane ("KBM-22" manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the other silane compound.

[0189] [Examples 6 to 10, Comparative Example 3] Spherical silica (Admatechs, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd., "KBM573").2 The silica particles were not mixed with 100g of water, but were spherical silica particles (Admatechs' SO-C1, average particle size 0.3 μm, specific surface area 10 m) that were surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical's KBM-573)). 2 A resin varnish was obtained in the same manner as in Examples 1 to 5 and Comparative Example 1, except that the amount added was changed as shown in the table.

[0190] [Examples 11 to 15, Comparative Example 4] Spherical silica (Admatechs, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd., "KBM573"). 2 The silica gel was prepared by treating the surface of spherical silica (Admatechs' 180 nmSX-C1, average particle size 0.18 μm, specific surface area 20 m2) with an inorganic filler (an amine-based alkoxysilane compound (Shin-Etsu Chemical's KBM-573)). 2 A resin varnish was obtained in the same manner as in Examples 1 to 5 and Comparative Example 1, except that a 1,2-diphenyldimethoxysilane ("KBM-202SS" manufactured by Shin-Etsu Chemical Co., Ltd.) was used as component (A) and the amount added was changed as shown in the table.

[0191] [Examples 16 to 20, Comparative Example 5] Spherical silica (Admatechs, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd., "KBM573"). 2 The amount of silica added was changed to 75 parts / g, and hollow silica (JGC Catalysts and Chemicals "BA-S", average particle size 3 μm, specific surface area 2.2 m) surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd. "KBM-573") was added. 2 A resin varnish was obtained in the same manner as in Examples 1 to 5 and Comparative Example 1, except that 25 parts ( / g) of glycerin was used.

[0192] [Example 21] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler was changed to 145 parts and 2 parts of a maleimide compound ("SLK-2700" manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution with a non-volatile content of 50% by mass) was added.

[0193] [Example 22] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler in Example 1 was changed to 145 parts, and 2 parts of a styryl resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution with a non-volatile content of 65% by mass) was added as another radical polymerizable compound.

[0194] [Example 23] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler in Example 1 was changed to 145 parts, and 2 parts of styryl resin (divinylbenzene copolymer prepared by the procedure described below, toluene solution with 50% nonvolatile content) was added as another radical polymerizable compound.

[0195] -Preparation of divinylbenzene copolymer- 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were charged into a 5.0 L reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added at 70 ° C. and reacted for 4 hours. After the polymerization solution was stopped with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, and the copolymer was recovered by degassing under reduced pressure at 60 ° C. The obtained copolymer was weighed, and it was confirmed that 896.7 g of divinylbenzene copolymer was obtained. The weight average molecular weight (Mw) of the divinylbenzene copolymer was 41,300.

[0196] [Example 24] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler was changed to 145 parts and 2 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a mixed solution of MEK and cyclohexanone with a non-volatile content of 30% by mass) was added as a polymer compound.

[0197] [Example 25] A resin varnish was obtained in the same manner as in Example 1, except that the amount of inorganic filler was changed to 145 parts, and 2 parts of polyimide resin (polyimide resin 1 prepared by the procedure below, cyclohexanone solution with 30% by mass of non-volatile content) was added as the polymer compound.

[0198] -Preparation of polyimide resin 1- In a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas inlet tube, 330.0 g of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (SABIC Innovative Plastics Japan, LLC., "BisDA-1000"), 1065.4 g of cyclohexanone, and 213.09 g of methylcyclohexane were charged and heated to 60 ° C. Next, 218.67 g of commercially available dimer diamine (Croda Japan, Inc., "PRIAMINE 1075") and 30.35 g of 3,5-diaminobenzoic acid (Nihon Junryo Pharmaceuticals, Inc., "3,5-DABA") were dropped, and the mixture was subjected to an imidization reaction at 140 ° C. for 12 hours to obtain a solution of polyimide resin 1 (non-volatile content 30.0%).

[0199] [Preparation Example 1: Preparation of resin sheet A having a resin composition layer thickness of 40 μm] A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish (resin composition) obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

[0200] [Preparation Example 2: Preparation of Cured Product B for Evaluation] The resin sheet A obtained in each of the examples and comparative examples was cured in an oven at 190° C. for 90 minutes. The support was peeled off from the resin sheet A taken out of the oven to obtain a cured product of the resin composition layer. The cured product was cut into a length of 80 mm and a width of 2 mm to be used as cured product B for evaluation.

[0201] [Test Example 1: Measurement of dielectric constant and dielectric loss tangent] For each evaluation cured product B, the dielectric constant (Dk) and the dielectric loss tangent (Df value) were measured by the cavity resonance perturbation method using an "HP8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. Measurements were performed on two test pieces, and the average was calculated.

[0202] [Test Example 2: Measurement of average thermal expansion coefficient] Each evaluation cured product B was cut into a length of 20 mm and a width of 6 mm to prepare an evaluation sample. The average coefficient of thermal expansion (CTE; ppm) of each evaluation sample was measured from 25°C to 150°C at a heating rate of 5°C / min using a Rigaku TMA device. The same test piece was measured twice, and the second value was recorded.

[0203] [Test Example 3: Measurement of melt viscosity] Each resin sheet A obtained in Preparation Example 1 was peeled off from the support and measured using a dynamic viscoelasticity measuring device G-3000 manufactured by UBM at a frequency of 1 Hz, a strain of 5 degrees, a load of 100 g, a heating rate of 5°C / min, and a temperature range of 60°C to 180°C.

[0204] The amounts (parts by mass) of components (A) to (G) used, including volatile components, of the resin varnishes (resin compositions) of the Examples and Comparative Examples, and the measurement results of the Test Examples are shown in the following Tables 1 to 5. In Tables 1 to 5, the non-volatile content (mass%) of each component is shown in the "NV" column.

[0205] [Table 1]

[0206] [Table 2]

[0207] [Table 3]

[0208] [Table 4]

[0209] [Table 5]

[0210] From the above, it was found that by using a resin composition containing (A) a silane compound represented by formula (A-1), (B) an epoxy resin, and (B) an active ester compound, it is possible to obtain a cured product that can achieve both a low dielectric tangent and a low melt viscosity. It was also found that this cured product has a low average coefficient of thermal expansion (CTE) and a low relative dielectric constant (Dk).

Claims

1. A resin composition for forming an interlayer insulating layer of a printed wiring board, comprising: (A) a silane compound represented by the following formula (A-1), (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, The component (A) contains diphenyldimethoxysilane, A resin composition, wherein the component (D) has been surface-treated with a surface treatment agent, and the surface treatment agent is an alkoxysilane compound different from the component (A). (2) ｎ ｳir ４－ｎ (2-1) (In the formula, R represents an alkyl group, Ar represents an aryl group, and n represents 1 or 2.)

2. A resin composition comprising: (A) a silane compound represented by the following formula (A-1), (B) an epoxy resin, (C) an active ester compound, (D) an inorganic filler, and (E) a radical polymerizable compound, The component (A) contains diphenyldimethoxysilane, A resin composition, wherein the component (D) has been surface-treated with a surface treatment agent, and the surface treatment agent is an alkoxysilane compound different from the component (A). (RO) n SiAr 4-n (A-1) (In the formula, R represents an alkyl group, Ar represents an aryl group, and n represents 1 or 2.)

3. 3. The resin composition according to claim 1, wherein the content of the component (A) is 0.05% by mass or more and 1% by mass or less, based on 100% by mass of the resin component in the resin composition.

4. The resin composition according to claim 1 or 2, wherein the alkoxysilane compound different from the component (A) includes an amino-silane coupling agent.

5. The resin composition according to claim 1 , further comprising (E) a radically polymerizable compound.

6. The resin composition according to claim 2 or 5, wherein the radical polymerizable compound (E) comprises a maleimide compound (E1).

7. The resin composition according to claim 6, wherein the maleimide compound (E1) comprises at least one selected from the group consisting of (E1-1a) maleimide compounds containing a trimethylindane skeleton, and (E1-2a) bismaleimide resins containing an aromatic ring skeleton directly bonded to a nitrogen atom of the maleimide group and containing three or more aromatic rings in the molecule.

8. The resin composition according to claim 2, which is used for forming an interlayer insulating layer of a printed wiring board.

9. A cured product of the resin composition according to claim 1 or 2.

10. A sheet-like laminate material comprising the resin composition according to claim 1 or 2.

11. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to claim 1 or 2 on the support.

12. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to claim 1 or 2.

13. A semiconductor device comprising the printed wiring board according to claim 12.

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