JP2017095599A - Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is cured to form a cured product capable of achieving a printed wiring board excellent in peel strength, glass transition temperature, thermal conductivity, flexural strength, and thermal expansion coefficient.SOLUTION: The resin composition contains an epoxy resin (A) represented by formula (1) and a maleimide compound (B). The resin composition preferably further contains a filler (C). In addition, the resin composition more preferably contains one or more selected from epoxy resins other than the epoxy resin (A), cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, or compounds having a polymerizable unsaturated group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a prepreg, the resin composition, a metal foil-clad laminate using the prepreg, a resin sheet, and a printed wiring board using the same.

  In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers and the like have been accelerated. As a result, various characteristics required for semiconductor package laminates used for printed wiring boards have become increasingly severe. The required properties include, for example, properties such as low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. However, so far, these required characteristics have not always been satisfied.

Conventionally, cyanate ester compounds have been known as resins for printed wiring boards that have excellent heat resistance and electrical characteristics. In recent years, resin compositions in which cyanate ester compounds are used in combination with epoxy resins, bismaleimide compounds, etc. are used in semiconductor plastic packages. Widely used for high-performance printed wiring board materials.
Further, as the multilayer printed wiring board is miniaturized and densified, the build-up layer used for the multilayer printed wiring board is made into multiple layers, and miniaturization and high density of the wiring are required. Along with this, studies have been actively conducted to reduce the thickness of the laminate used for this build-up layer.
Furthermore, since the problem of expansion of warp occurs in the multilayer printed wiring board, a high glass transition temperature is required for the resin composition used as the material of the insulating layer.

International Publication No. 2013/065694 Pamphlet International Publication No. 2014/203866 Pamphlet

  For example, Patent Documents 1 and 2 propose a resin composition composed of a cyanate ester compound and an epoxy resin that are excellent in properties such as adhesion, low water absorption, moisture absorption heat resistance, and insulation reliability. Since the heat resistance is still insufficient, a resin composition for the purpose of further improving the properties has been studied. Among these, epoxy resins are resins that are generally excellent in adhesion, fluidity, and processability, and studies have been conducted for the purpose of imparting further characteristics using various epoxy resins having different structures.

  An object of the present invention is to provide a resin composition capable of realizing a printed wiring board not only excellent in peel strength but also excellent in glass transition temperature, thermal conductivity, bending strength and low thermal expansion. An object of the present invention is to provide a prepreg and a resin sheet used, and a metal foil-clad laminate or a printed wiring board using the prepreg.

  As a result of intensive studies on the above problems, the present inventors have used a resin composition containing an epoxy resin (A) and a maleimide compound (B) represented by the formula (1), thereby achieving high peel strength and glass. The inventors have found that a cured product having a transition temperature, thermal conductivity, bending strength, and low thermal expansibility can be obtained, and reached the present invention. That is, the present invention is as follows.

1. A resin composition containing an epoxy resin (A) represented by the following formula (1) and a maleimide compound (B).

2. The content of the epoxy resin (A) in the resin composition is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content. The resin composition described in 1.

3. Furthermore, containing a filler (C). Or 2. The resin composition described in 1.

4). Further, an epoxy resin other than the epoxy resin (A) represented by the formula (1), a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group Among them, any one or more types are contained. ~ 3. The resin composition as described in any one of these.

5. 2. Content in the resin composition of the said filler (C) is 50-1600 mass parts with respect to 100 mass parts of resin solid content. Or 4. The resin composition described in 1.

6). 1. Substrate and impregnated or coated on the substrate ~ 5. The prepreg which has a resin composition as described in any one of these.

7). 5. At least one or more laminated. A metal foil-clad laminate comprising the prepreg according to 1) and a metal foil disposed on one or both sides of the prepreg.

8). 1. disposed on the support and the surface of the support; ~ 5. A resin sheet comprising the resin composition according to any one of the above.

9. And an insulating layer and a conductor layer formed on the surface of the insulating layer. ~ 5. The printed wiring board containing the resin composition as described in any one of these.

  According to the present invention, it is possible to realize a prepreg, a resin sheet, a metal foil-clad laminate, etc. having high peel strength, glass transition temperature, thermal conductivity, bending strength and low thermal expansion, so that high-performance printed wiring A plate can be realized, and its industrial practicality is extremely high.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

The epoxy resin (A) used in the present embodiment is represented by the following formula (1).

A commercially available epoxy resin (A) represented by the formula (1) may be used. For example, diallyl bisphenol S-type epoxy resin manufactured by Nippon Kayaku Co., Ltd. represented by the following formula (2), RE- DABS can be preferably used.

  The content of the epoxy resin (A) represented by the formula (1) in the resin composition of the present embodiment can be appropriately set according to desired properties, and is not particularly limited, but the resin in the resin composition When solid content is 100 mass parts, 1-90 mass parts is preferable. When content is the range of 1-90 mass parts, the resin composition which has high plating peel strength, a low thermal expansion coefficient, and high thermal conductivity is obtained. Here, unless otherwise specified, “resin solid content in the resin composition” means a component in the resin composition excluding the solvent and filler (C), and the resin solid content is 100 parts by mass. The total of the components excluding the solvent and the filler (C) in the resin composition is 100 parts by mass.

  As the maleimide compound (B) used in the present embodiment, generally known compounds can be used as long as they have one or more maleimide groups in one molecule. For example, 4,4-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl -4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4 -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethane maleimide, novolac maleimide, biphenylaralkyl maleimide, and these maleimide compounds Prepolymer Or although prepolymer of the maleimide compound and amine compound, but is not particularly limited. These maleimide compounds can be used alone or in combination. Of these, novolac maleimide compounds and biphenylaralkyl maleimide compounds are particularly preferred. The content of the maleimide compound in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited. However, when the resin solid content in the resin composition is 100 parts by mass, 1 -90 mass parts is preferable. When the content is in the range of 1 to 90 parts by mass, a resin composition having an excellent glass transition temperature is obtained.

As a filler (C) used for this embodiment, a well-known thing can be used suitably, The kind is not specifically limited, What is generally used in this industry can be used suitably. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride , Aluminum nitride, Barium sulfate, Aluminum hydroxide, Aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated and part of crystal water is reduced), Boehmite, Magnesium hydroxide and other metal hydrates, Oxidation Molybdenum compounds such as molybdenum and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C -Glass, L-glass, D-glass, S-glass, M-glass 20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, styrene type, butadiene type Organic type fillers such as rubber powder such as acrylic type, core shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder. These fillers can be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using these fillers, characteristics such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

  The content of the filler (C) in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but the resin solid content in the resin composition is 100 parts by mass. In this case, 50 to 1600 parts by mass are preferable. The moldability of a resin composition becomes favorable because content is 50-1600 mass parts.

  Here, when using the filler (C), it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As the silane coupling agent, those generally used for inorganic surface treatment can be suitably used, and the type thereof is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxylane, γ-glycidoxypropyltrimethoxysilane, β- (3,4) -Epoxycyclohexyl) Epoxysilane such as ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinylsilane such as vinyl-tri (β-methoxyethoxy) silane, N-β- (N-vinylbenzylaminoethyl)- Cationic silanes such as γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes and the like can be mentioned. A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. Moreover, as a wet dispersing agent, what is generally used for coating materials can be used suitably, The kind is not specifically limited. Preferably, a copolymer-based wetting and dispersing agent is used, and specific examples thereof include Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903 manufactured by Big Chemie Japan Co., Ltd. , BYK-W940 and the like. Wet dispersants can be used alone or in combination of two or more.

Furthermore, in the resin composition of the present embodiment, an epoxy resin other than the epoxy resin (A) represented by the formula (1) (hereinafter referred to as “other epoxy resin”) as long as the desired characteristics are not impaired. And a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and the like.
By using these in combination, desired properties such as flame retardancy and low dielectric property of a cured product obtained by curing the resin composition can be improved.

  The other epoxy resin is not represented by the formula (1), and any known epoxy resin having two or more epoxy groups in one molecule can be used as appropriate. The type is not particularly limited. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolak Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic ester Carboxy resin, a polyol type epoxy resins, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds of the double bonds epoxidized in butadiene, such as a compound obtained by reaction of a hydroxyl-group-containing silicon resin with epichlorohydrin. Among these epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance. These epoxy resins can be used alone or in combination of two or more.

  The cyanate ester compound is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).

（式中、Ａｒ_１は、各々独立に、置換基を有してもよいフェニレン基、置換基を有してもよいナフチレン基又は置換基を有してもよいビフェニレン基を表す。Ｒａは各々独立に水素原子、置換基を有してもよい炭素数１〜６のアルキル基、置換基を有してもよい炭素数６〜１２のアリール基、置換基を有してもよい炭素数１〜４のアルコキシル基、炭素数１〜６のアルキル基と炭素数６〜１２のアリール基とが結合した置換基を有してもよいアラルキル基又は炭素数１〜６のアルキル基と炭素数６〜１２のアリール基とが結合した置換基を有してもよいアルキルアリール基のいずれか一種から選択される。ｐはＡｒ_１に結合するシアナト基の数を表し、１〜３の整数である。ｑはＡｒ_１に結合するＲａの数を表し、Ａｒ_１がフェニレン基の時は４−ｐ、ナフチレン基の時は６−ｐ、ビフェニレン基の時は８−ｐである。ｔは平均繰り返し数を表し、０〜５０の整数であり、ｔが異なる化合物の混合物であってもよい。Ｘは、各々独立に、単結合、炭素数１〜５０の２価の有機基（水素原子がヘテロ原子に置換されていてもよい）、窒素数１〜１０の２価の有機基（−Ｎ−Ｒ−Ｎ−など）、カルボニル基（−ＣＯ−）、カルボキシ基（−Ｃ（＝Ｏ）Ｏ−）、カルボニルジオキサイド基（−ＯＣ（＝Ｏ）Ｏ−）、スルホニル基（−ＳＯ_２−）、或いは、２価の硫黄原子又は２価の酸素原子のいずれか一種から選択される。） For example, what is represented by General formula (3) is mentioned.

(In the formula, each Ar ₁ independently represents a phenylene group that may have a substituent, a naphthylene group that may have a substituent, or a biphenylene group that may have a substituent. Ra represents each. Independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent A C 1-4 alkoxyl group, an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent, or an alkyl group having 1 to 6 carbon atoms and a carbon number 6 Is selected from any one of an alkylaryl group optionally having a substituent bonded to an aryl group of -12, p is the number of cyanato groups bonded to Ar ₁ and is an integer of 1-3. .q represents the number of Ra to bind to Ar _1, Ar ₁ is a phenylene group The time is 4-p, the time is 6-p for a naphthylene group, and the time is 8-p for a biphenylene group, where t represents an average number of repetitions and is an integer from 0 to 50, where t is a mixture of different compounds. X is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a divalent organic group having 1 to 10 nitrogen atoms. Groups (—N—R—N—, etc.), carbonyl groups (—CO—), carboxy groups (—C (═O) O—), carbonyl dioxide groups (—OC (═O) O—), sulfonyl groups (—SO ₂ —), or a divalent sulfur atom or a divalent oxygen atom.

The alkyl group in Ra of the general formula (3) may have either a chain structure or a cyclic structure (cycloalkyl group or the like).
The hydrogen atom in the alkyl group in the general formula (3) and the aryl group in Ra may be substituted with a halogen atom such as fluorine or chlorine, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethyl. A propyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like can be mentioned.
Specific examples of the aryl group include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluoro. A phenyl group, a methoxyphenyl group, o-, m- or p-tolyl group and the like can be mentioned. Furthermore, examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
Specific examples of the divalent organic group represented by X in the general formula (3) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, and a dimethylmethylene group. Examples thereof include a phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidodiyl group. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as fluorine or chlorine, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the general formula (3) include an imino group and a polyimide group.

（式中、Ａｒ_２はフェニレン基、ナフチレン基及びビフェニレン基のいずれか一種から選択される。を表す。Ｒｂ、Ｒｃ、Ｒｆ、Ｒｇは各々独立に水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、トリフルオロメチル基及びフェノール性ヒドロキシ基が少なくとも１個置換されたアリール基のいずれか一種から選択される。Ｒｄ、Ｒｅは各々独立に水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、炭素数１〜４のアルコキシル基及びヒドロキシ基のいずれか一種から選択される。ｕは０〜５の整数を示すが、ｕが異なる化合物の混合物であってもよい。）

（式中、Ａｒ_３はフェニレン基、ナフチレン基又はビフェニレン基のいずれか一種から選択される。Ｒｉ、Ｒｊは各々独立に水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ベンジル基、炭素数１〜４のアルコキシル基、ヒドロキシ基、トリフルオロメチル基及びシアナト基が少なくとも１個置換されたアリール基のいずれか一種から選択される。ｖは０〜５の整数を示すが、ｖが異なる化合物の混合物であってもよい。） Moreover, as X in General formula (3), what is a structure represented by following General formula (4) or following General formula (5) is mentioned.

(In the formula, Ar ₂ represents one selected from a phenylene group, a naphthylene group, and a biphenylene group. Rb, Rc, Rf, and Rg are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, It is selected from any one of an aryl group having 6 to 12 carbon atoms, an aryl group substituted with at least one phenolic hydroxy group, and Rd and Re are each independently a hydrogen atom, 6 is selected from any one of an alkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group, u is an integer of 0 to 5, but u is a different compound. It may be a mixture.)

(In the formula, Ar ₃ is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms. A group, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group and an aryl group substituted with at least one cyanato group, v is an integer of 0 to 5; As shown, it may be a mixture of compounds with different v.)

（式中、ｚは４〜７の整数を表す。Ｒｋは各々独立に水素原子又は炭素数１〜６のアルキル基を表す。）
一般式（４）のＡｒ_２及び一般式（５）のＡｒ_３の具体例としては、１，４−フェニレン基、１，３−フェニレン基、４，４’−ビフェニレン基、２，４’−ビフェニレン基、２，２’−ビフェニレン基、２，３’−ビフェニレン基、３，３’−ビフェニレン基、３，４’−ビフェニレン基、２，６−ナフチレン基、１，５−ナフチレン基、１，６−ナフチレン基、１，８−ナフチレン基、１，３−ナフチレン基、１，４−ナフチレン基等が挙げられる。
一般式（４）のＲｂ〜Ｒｇ及び一般式（５）のＲｉ、Ｒｊにおけるアルキル基及びアリール基は一般式（３）で記載したものと同様である。 Furthermore, as X in General formula (3), the bivalent group represented by a following formula is mentioned.

(In the formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Specific examples of Ar _{2 in the} general formula (4) and Ar _{3 in} the general formula (5) include 1,4-phenylene group, 1,3-phenylene group, 4,4′-biphenylene group, 2,4′- Biphenylene group, 2,2′-biphenylene group, 2,3′-biphenylene group, 3,3′-biphenylene group, 3,4′-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1 , 6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group and the like.
The alkyl group and aryl group in Rb to Rg of the general formula (4) and Ri and Rj of the general formula (5) are the same as those described in the general formula (3).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (3) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1- Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1 -Cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- ( 4-cyanphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, -Cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2 -Ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1- Cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanato Benzophenone, 1-cyanato-2,6-di-tert-butyl Tylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-si Anatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanatobiff Enyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4 -Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) Propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-dimethyl) Phenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) penta 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1,1-bis (4-cyanatophenyl) -2, 2-dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2,2 -Bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3-dimethyl Butane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3-bis ( 4-cyanatophenyl) 2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4-bis (4 -Cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylhexane, 3 , 3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis (4-si Anatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenylethane, bis (4-cyanatofe Nyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3-bis [ 2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzophenone, , 3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanatophenyl) adamantane 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthalein), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (cyanate of o-cresolphthalein) G), 9,9′-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) Fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α ′ -Tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4 , 6-Tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino) -1,3,5 − Liazine, bis (N-4-cyanato-2-methylphenyl) -4,4′-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4,4′-oxydiphthalimide, bis ( N-4-cyanatophenyl) -4,4′-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4 ′-(hexafluoroisopropylidene) diphthalimide, tris (3 5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-cyanato) Phenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanatofe) L) Indoline-2-one, 2-phenyl-3,3-bis (4-cyanatophenyl) indoline-2-one, phenol novolac resin or cresol novolac resin (by known methods, phenol, alkyl-substituted phenol or halogen) Substituted phenol and formaldehyde compounds such as formalin and paraformaldehyde in an acidic solution), trisphenol novolak resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (A product obtained by reacting a fluorenone compound with 9,9-bis (hydroxyaryl) fluorene in the presence of an acidic catalyst), a phenol aralkyl resin, a cresol aralkyl resin, a naphthol aralkyl resin or a biphenyl aralkyl Resin (by known _{methods, Ar 2 - (CH 2 Y} ) which the bishalogenomethyl compounds represented by ₂ and a phenolic compound is reacted with an acid catalyst or no _{catalyst, Ar 2 - (CH 2 OR} ) A bis (alkoxymethyl) compound represented by ₂ or a bis (hydroxymethyl) compound represented by Ar ₂ — (CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, Or an aromatic aldehyde compound, an aralkyl compound and a phenol compound polycondensed), a phenol-modified xylene formaldehyde resin (a product obtained by reacting a xylene formaldehyde resin and a phenol compound in the presence of an acidic catalyst by a known method) Modified naphthalene formaldehyde resin (by known methods, naphthalene formaldehyde) Phenolic resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (one molecule of phenolic hydroxy group by a known method) Examples thereof include those obtained by cyanating a phenolic resin such as a polyhydric hydroxynaphthalene compound having two or more compounds in the presence of a basic catalyst and the like in the same manner as described above. It is not something. These cyanate ester compounds can be used alone or in combination. The cured resin using these cyanate ester compounds has excellent properties such as plating adhesion.

  Among them, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, biphenyl aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, adamantane skeleton type cyanate ester A compound is preferable, and a naphthol aralkyl cyanate compound is particularly preferable because of excellent flame retardancy, high curability, and a low thermal expansion coefficient of a cured product. Particularly preferred.

  The content of the cyanate ester compound in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but when the resin solid content in the resin composition is 100 parts by mass 1 to 90 parts by mass are preferable.

  As the phenol resin, generally known resins can be used as long as they are phenol resins having two or more hydroxy groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenolaralkyl type phenolic resin, naphthol aralkyl type Phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin Alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

  As the oxetane resin, generally known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) There are no particular restrictions. These oxetane resins can be used alone or in combination.

  As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical), etc. There are no particular restrictions. These benzoxazine compounds can be used alone or in combination.

  As the compound having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, Mono- or polyhydric alcohol (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol Epoxy (meth) acrylates such as A-type epoxy (meth) acrylate and bisphenol F-type epoxy (meth) acrylate, benzocyclobutene resin, (bis) male De resins, but is not particularly limited. These compounds having an unsaturated group can be used alone or in combination.

Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening rate suitably as needed. As this hardening accelerator, what is generally used as hardening accelerators, such as a cyanate ester compound and an epoxy resin, can be used suitably, The kind is not specifically limited. Specific examples thereof include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, acetylacetone iron, nickel octylate, manganese octylate and the like, phenol, xylenol, cresol, resorcin, catechol, octylphenol, Phenol compounds such as nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl Imidazoles such as 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like Derivatives such as adducts of carboxylic acids or acid anhydrides of dazoles, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salts Compounds, phosphorus compounds such as diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxy Examples thereof include peroxides such as carbonates, and azo compounds such as azobisisobutyronitrile. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.
The amount of the curing accelerator used can be appropriately adjusted in consideration of the degree of curing of the resin, the viscosity of the resin composition, and the like, and is not particularly limited, but usually the resin solid content in the resin composition is 100 parts by mass. In this case, it is 0.005 to 10 parts by mass.

  Furthermore, the resin composition of the present embodiment includes various thermosetting resins such as other thermosetting resins, thermoplastic resins and oligomers thereof, elastomers and the like within a range in which desired characteristics are not impaired. Various additives and the like can be used in combination. These are not particularly limited as long as they are generally used. Examples of flame retardant compounds include bromine compounds such as 4,4′-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, silicone compounds Etc. Various additives include UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, and dispersions. Agents, leveling agents, brighteners, polymerization inhibitors and the like. These may be used alone or in combination of two or more as desired.

  In addition, the resin composition of this embodiment can use an organic solvent as needed. In this case, the resin composition of the present invention can be used as an embodiment (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it dissolves or is compatible with at least a part, preferably all of the above-mentioned various resin components, and the kind thereof is not particularly limited. . Specifically, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate And ester solvents such as methyl methoxypropionate and methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

  The resin composition of this embodiment can be prepared according to a conventional method, and uniformly contains the epoxy resin (A) represented by the formula (1), the maleimide compound (B), and other optional components described above. If it is a method by which a resin composition is obtained, the adjustment method will not be specifically limited. For example, the epoxy resin (A) represented by the formula (1) and the maleimide compound (B) are sequentially mixed in a solvent and sufficiently stirred, whereby the resin composition of this embodiment can be easily adjusted.

  In preparing the resin composition, a known process (such as stirring, mixing, kneading process) for uniformly dissolving or dispersing each component can be performed. For example, when uniformly dispersing the filler (C), the dispersibility with respect to the resin composition is enhanced by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving / spinning mixing device.

The resin composition of this embodiment can be used as an insulating layer of a printed wiring board and a semiconductor package material. For example, a prepreg can be obtained by impregnating or applying a solution obtained by dissolving the resin composition of the present invention in a solvent to a base material and drying.
Moreover, it can be set as a resin sheet by drying the solution which melt | dissolved the resin composition of this embodiment in the solvent. The resin sheet can be used as a build-up film or a dry film solder resist.
Moreover, the resin composition of this embodiment can also be used in the uncured state which dried the solvent, and can also be used in the semi-cured (B-stage) state as needed.

  Hereinafter, the prepreg of this embodiment will be described in detail. The prepreg of this embodiment is obtained by impregnating or coating the base material with the resin composition of this embodiment described above. The manufacturing method of a prepreg will not be specifically limited if it is a method of manufacturing a prepreg combining the resin composition of this embodiment, and a base material. Specifically, after impregnating or applying the resin composition of the present embodiment to the substrate, the prepreg of the present embodiment is semi-cured by a method such as drying at 120 to 220 ° C. for about 2 to 15 minutes. Can be manufactured. At this time, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition (including the filler (C)) relative to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass.

  As a base material used when manufacturing the prepreg of this embodiment, the well-known thing used for various printed wiring board materials can be used. For example, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass and spherical glass, inorganic fibers other than glass such as quartz, organic materials such as polyimide, polyamide and polyester Although woven fabrics, such as a fiber and liquid crystal polyester, are mentioned, It does not specifically limit to these. As the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat and the like are known, but any of them may be used. A base material can be used individually by 1 type or in combination of 2 or more types. Further, the thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for use in a laminate, and a woven fabric that has been subjected to ultra-opening treatment or plugging treatment is particularly dimensionally stable. From the viewpoint of Further, a glass woven fabric surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferable from the viewpoint of moisture absorption heat resistance. A liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics.

In addition, the metal foil-clad laminate of the present embodiment is obtained by laminating and forming at least one prepreg as described above and placing metal foil on one or both sides thereof. Specifically, it can be produced by laminating one or a plurality of the aforementioned prepregs, placing a metal foil such as copper or aluminum on one side or both sides thereof, and laminating. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Copper foil, such as a rolled copper foil and an electrolytic copper foil, is preferable. Moreover, although the thickness of metal foil is not specifically limited, 2-70 micrometers is preferable and 3-35 micrometers is more preferable. As a molding condition, a general laminated board for a printed wiring board and a multilayer board can be applied. For example, by using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc., by laminating and molding at a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ^2. The metal foil-clad laminate of the present invention can be manufactured. Moreover, it can also be set as a multilayer board by carrying out the lamination | stacking shaping | molding combining said prepreg and the wiring board for inner layers produced separately. As a method for producing a multilayer board, for example, a 35 μm copper foil is disposed on both surfaces of one prepreg described above, laminated under the above conditions, an inner layer circuit is formed, and blackening treatment is performed on this circuit. The inner circuit board is then formed, and then the inner circuit board and the prepreg are alternately arranged one by one, and the copper foil is further disposed on the outermost layer, and preferably laminated under the above conditions, preferably under vacuum By doing so, a multilayer board can be produced.

  And the metal foil tension laminated board of this embodiment can be used conveniently as a printed wiring board. The printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, a metal foil clad laminate such as the copper clad laminate described above is prepared. Next, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is stacked on the outer surface. Then, it is integrally molded by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling for the through holes and via holes in the multilayer laminate, a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit and the metal foil for the outer layer circuit. A printed wiring board is manufactured by performing an etching process on the metal foil for forming an outer layer circuit.

  The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the above-described resin composition of the present embodiment. That is, the prepreg of the present embodiment described above (the base material and the resin composition of the present embodiment impregnated or coated thereon), the layer of the resin composition of the metal foil-clad laminate of the present embodiment described above (of the present invention). The layer made of the resin composition is composed of an insulating layer containing the resin composition of the present embodiment.

  On the other hand, the resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the above resin composition in a solvent to a support and drying it. Although it does not specifically limit as a support body used here, For example, the mold release agent was apply | coated to the surface of a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and these films. Examples thereof include organic film base materials such as release films and polyimide films, conductive foils such as copper foil and aluminum foil, and plate-like inorganic films such as glass plates, SUS plates, and FRP. As an application method, for example, a solution obtained by dissolving the above resin composition in a solvent is applied onto a support with a bar coater, a die coater, a doctor blade, a baker applicator, etc., so that the support and the resin sheet are integrated. The method of producing the laminated sheet which became will be mentioned. Moreover, it can also be set as a single layer sheet (resin sheet) by peeling or etching a support body from a lamination sheet after drying. In addition, a support is used by forming a sheet in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried. A single layer sheet (resin sheet) can also be obtained.

  In the production of the resin sheet (single layer or laminated sheet) of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition at a high temperature. When it exists, since hardening of a resin composition advances, 1 to 90 minutes are preferable at the temperature of 20 to 200 degreeC. Further, the thickness of the resin layer of the resin sheet (single layer or laminated sheet) of the present embodiment can be adjusted by the concentration of the resin composition solution and the coating thickness of the present embodiment, and is not particularly limited. Since the solvent tends to remain at the time of drying when the coating thickness is thick, 0.1 to 500 μm is preferable.

  Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these.

(Synthesis Example 1) Synthesis of cyanate ester compound 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (OH group conversion 1.28 mol) and triethylamine 194.6 g (1.92 mol) (based on 1 mol of hydroxy group) 1.5 mol) was dissolved in 1800 g of dichloromethane.
125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group) ), 1205.9 g of water was poured over 30 minutes while stirring at a liquid temperature of −2 to −0.5 ° C. After the completion of the pouring of solution 1, after stirring at the same temperature for 30 minutes, a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. Over time. After the end of pouring the solution 2, the reaction was completed by stirring at the same temperature for 30 minutes.
Thereafter, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water. The electric conductivity of the waste water in the fifth washing with water was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product). The obtained SNCN had a mass average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed an absorption of 2250 cm ⁻¹ (cyanate ester group) and no absorption of a hydroxy group.

Example 1
50 parts by mass of diallyl bisphenol S-type epoxy resin (RE-DABS, manufactured by Nippon Kayaku Co., Ltd.) represented by the following formula (2), phenol novolac-type bismaleimide compound (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.) 50 parts by mass, 100 parts by mass of fused silica (SC2050MB, manufactured by Admatex) and 0.15 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated on a 0.1 mm thick E glass woven fabric, and dried by heating at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 50 mass%.

8 sheets of the obtained prepregs are stacked and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) is placed up and down, and laminated molding at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 120 minutes. A metal foil-clad laminate with an insulating layer thickness of 0.8 mm was obtained. Using the obtained metal foil-clad laminate, evaluation of plating peel strength, copper foil peel strength, glass transition temperature, thermal conductivity, bending strength, and thermal expansion coefficient was performed. The results are shown in Table 1.

(Example 2)
In Example 1, except that 25 parts by mass of diallyl bisphenol S-type epoxy resin represented by the formula (2) was used and 25 parts by mass of SNCN obtained in Synthesis Example 1 was used, the thickness was the same as in Example 1. A metal foil-clad laminate with a thickness of 0.8 mm was obtained. Using the obtained metal foil-clad laminate, the glass transition temperature, the coefficient of thermal expansion, and the bending strength were evaluated. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, instead of using 50 parts by mass of the epoxy resin represented by formula (2), 50 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) was used. Obtained a metal foil-clad laminate having a thickness of 0.8 mm in the same manner as in Example 1. Using the obtained metal foil-clad laminate, evaluation of plating peel strength, copper foil peel strength, glass transition temperature, thermal conductivity, bending strength, and thermal expansion coefficient was performed. The results are shown in Table 1.

(Comparative Example 2)
In Example 2, instead of using 25 parts by mass of the epoxy resin represented by the formula (2), 25 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) was used. Obtained a metal foil-clad laminate having a thickness of 0.8 mm in the same manner as in Example 3. Evaluation of glass transition temperature, thermal conductivity, and bending strength was performed using the obtained metal foil-clad laminate. The results are shown in Table 2.

(Measurement method and evaluation method)
[Plating peel strength]
The obtained eight-layer metal foil-clad laminate was subjected to electroless copper plating process (used chemical names: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL) manufactured by Uemura Kogyo Co., Ltd. -3-APEA ver.2), electroless copper plating of about 0.8 μm was applied and dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm, and drying was performed at 180 ° C. for 1 hour. Thus, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was prepared and evaluated. The adhesive strength of the plated copper was measured three times according to JIS C6481, and the average value was obtained.
[Copper foil peel strength]
About the obtained eight-layer metal foil-clad laminate, according to JIS C6481, a test piece with a metal foil of 12 μm (30 mm × 150 mm × 0.8 mm) was used, and the peel strength of the copper foil was measured with a test number of 3. Measurement was made and the average of the lower limit values was taken as the measured value.
[Glass-transition temperature]
With respect to the obtained 8-layer metal foil-clad laminate, the glass transition temperature was measured by the DMA method with a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481.
[Thermal conductivity]
The density of the obtained eight-layer metal foil-clad laminate was measured, the specific heat was measured by DSC (TA Instrument Q100 type), and the thermal diffusivity was measured by a xenon flash analyzer (Bruker: LFA447 Nanoflash). . The thermal conductivity was calculated from the following formula.
Thermal conductivity (W / m · K) = density (kg / m ³ ) × specific heat (kJ / kg · K) × thermal diffusivity (m ² / S) × 1000
[Bending strength]
After removing the copper foils on both sides of the obtained 8-layer metal foil-clad laminate by etching, using a test piece (50 mm × 25 mm × 0.8 mm) in accordance with JIS C6481, bending strength with a test number of 5 And the average of the maximum values was taken as the measured value.
[Linear thermal expansion coefficient]
The thermal expansion coefficient of the glass cloth in the longitudinal direction was measured for the insulating layer of the laminated plate by the TMA method (Thermo-mechanical analysis) defined in JlS C 6481, and the value was obtained. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, the thermomechanical analyzer (manufactured by TA Instruments) at 40 ° C. to 340 ° C. at 10 ° C. per minute. The temperature was raised and the linear thermal expansion coefficient (ppm / ° C.) from 60 ° C. to 120 ° C. was measured.

  As is apparent from Tables 1 and 2, by using the resin composition of the present invention, a prepreg and printed wiring board having high peel strength, glass transition temperature, thermal conductivity, low thermal expansion and high bending strength can be obtained. It was confirmed that it could be realized.

  As described above, the resin composition of the present invention is used in various applications such as electrical / electronic materials, machine tool materials, aviation materials, etc. Widely and effectively usable as resist, build-up laminated board material, etc. Especially, it can be used particularly effectively as printed wiring board material for high integration and high density in recent information terminal equipment and communication equipment. It is. In addition, since the laminate and the metal foil-clad laminate of the present invention have excellent performance in peel strength, glass transition temperature, thermal conductivity, bending strength and low thermal expansion, their industrial practicality is extremely high. It will be a thing.

Claims (9)

A resin composition containing an epoxy resin (A) represented by the following formula (1) and a maleimide compound (B).

  The resin composition of Claim 1 whose content in the resin composition of the said epoxy resin (A) is 1-90 mass parts with respect to 100 mass parts of resin solid content.   Furthermore, the resin composition of Claim 1 or 2 containing a filler (C).   Further, an epoxy resin other than the epoxy resin (A) represented by the formula (1), a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group Among these, the resin composition as described in any one of Claims 1-3 containing any 1 or more types.   The resin composition of Claim 3 or 4 whose content in the resin composition of the said filler (C) is 50-1600 mass parts with respect to 100 mass parts of resin solid content.   The prepreg which has a base material and the resin composition as described in any one of Claims 1-5 impregnated or apply | coated to this base material.   A metal foil-clad laminate comprising at least one prepreg laminated according to claim 6 and a metal foil disposed on one side or both sides of the prepreg.   The resin sheet which has a resin composition as described in any one of Claims 1-5 distribute | arranged to the support body and the surface of this support body.   The printed wiring board which has an insulating layer and the conductor layer formed in the surface of this insulating layer, and this insulating layer contains the resin composition as described in any one of Claims 1-5.