JP6531910B2 - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Description

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

  BACKGROUND In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminate for a semiconductor package used for a printed wiring board are becoming increasingly severe. Examples of the required properties include properties such as low water absorption, hygroscopic heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, high plating peel strength and the like. However, so far, these required characteristics have not always been satisfied.

  Conventionally, cyanate ester compounds are known as resins for printed wiring boards which are excellent in heat resistance and electrical properties, and resin compositions in which bismaleimide compounds, epoxy resins and the like are used in combination with cyanate ester compounds have recently been used for semiconductor plastic packaging It is widely used for high-performance printed wiring board materials etc. A resin composition using a common bismaleimide compound has excellent properties such as high heat resistance, chemical resistance, and electrical properties, but the properties are insufficient in terms of hygroscopic heat resistance, low water absorption, etc. Since there are cases, investigations of various maleimide compounds having different structures are being conducted for the purpose of further improving the properties.

JP 7-53864 A Patent No. 4784066

  A resin composition consisting of a bismaleimide compound having an alkyl group in the side chain of a benzene nucleus has been proposed as a maleimide compound excellent in properties such as moisture absorption heat resistance and low dielectricity (see, for example, Patent Documents 1 and 2). Since improvement in properties such as peel strength and thermal expansion coefficient of cured products is still insufficient, further improvement in heat resistance and hygroscopic heat resistance is required.

  An object of the present invention is to provide a resin composition capable of realizing a printed wiring board excellent in heat resistance, peel strength and thermal expansion coefficient, and a prepreg, a single layer or a laminated sheet using this, and a resin composition An object of the present invention is to provide a metal foil-clad laminate, a printed wiring board or the like using the prepreg.

As a result of intensive studies on the above problems, the present inventors have found that the resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1) can be used for heat resistance. It has been found that a cured product having excellent properties, peel strength and thermal expansion coefficient can be obtained, and the present invention has been achieved. That is, the present invention is as follows.

1. A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).

2. When resin solid content in the said resin composition is 100 mass parts, content of a bismaleimide compound (B) is 1-90 mass parts, 1. The resin composition as described in.

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

4. Furthermore, among the group selected from maleimide compounds other than the bismaleimide compound (B) represented by the formula (1), epoxy resins, phenol resins, oxacene resins, benzoxazine compounds, compounds having a polymerizable unsaturated group Or any one or more of them. ~ 3. The resin composition as described in any one of these.

5. 2. The content of the filler (C) in the resin composition is 50 to 1600 parts by mass, when the resin solid content in the resin composition is 100 parts by mass. Or 4. The resin composition as described in.

6.1. To 5. The prepreg formed by impregnating or apply | coating the resin composition as described in any one to a base material.

7.6. A metal foil-clad laminate obtained by laminating at least one or more of the prepregs described in 1 and laminating a metal foil on one side or both sides thereof.

8.1. To 5. The resin sheet formed by apply | coating and drying the resin composition as described in any one of these to the surface of a support body.

9. A printed wiring board comprising an insulating layer and a conductor layer formed on the surface of the insulating layer, wherein the insulating layer comprises: To 5. The printed wiring board containing the resin composition as described in any one of these.

  According to the present invention, a prepreg, a resin sheet, a metal foil-clad laminate, etc. excellent in heat resistance, peel strength, thermal expansion coefficient and solder heat resistance can be realized, and its industrial practicability is extremely high. is there.

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

  The cyanate ester compound (A) used in the present embodiment is not particularly limited as long as it is a resin having in the molecule an aromatic moiety substituted with at least one cyanato group (cyanate 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 (2) is mentioned.

(In the formula, Ar ₁ each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a biphenylene group which may have a substituent. 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, carbon number 1 which may have a substituent -4 alkoxyl group, an aralkyl group which may have a substituent in which an alkyl group having 1 to 6 carbon atoms is bonded to an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 6 carbon atoms and 6 carbon atoms It is selected from any one of an alkyl aryl group optionally having a substituent to which an aryl group of 12 to 12 is bonded, p represents the number of cyanato groups bonded to Ar ₁ and is an integer of 1 to 3 .q represents the number of Ra to bind to Ar _1, Ar ₁ is a phenylene group The time is 4-p, 6-p for the naphthylene group, and 8-p for the biphenylene group, t is an average number of repeating, is an integer from 0 to 50, and t is a mixture of different compounds. X each independently represents 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 having 1 to 10 nitrogen atoms. Group (-N-R-N-, etc.), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group (-OC (= O) O-), sulfonyl group (-SO _2- ), or selected from any one of a divalent sulfur atom and a divalent oxygen atom.)

The alkyl group at Ra of General Formula (2) may have either a chain structure or a cyclic structure (such as a cycloalkyl group).
The hydrogen atom in the alkyl group in the general formula (2) 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 group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethyl group A propyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group etc. are mentioned.
Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluoro A phenyl group, a methoxyphenyl group, o-, m- or p- tolyl group etc. are mentioned. Furthermore, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like can be mentioned.
Specific examples of the divalent organic group in X in the general formula (2) include an alkylene group such as methylene, ethylene, trimethylene and propylene, a cyclopentylene group, a cyclohexylene group, and a trimethylcyclohexylene group. Examples thereof include divalent organic groups having an aromatic ring such as a cycloalkylene group, a biphenylyl methylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalide diyl group. The hydrogen atom in the divalent organic group may be substituted by 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 in the general formula (2) 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 (2), what is a structure represented by following General formula (3) or following General Formula (4) is mentioned.

(Wherein, Ar ₂ is selected from any one of a phenylene group, a naphthylene group and a biphenylene group. Rb, Rc, Rf and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, The aryl group is selected from any one of an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, and an aryl group in which at least one phenolic hydroxy group is substituted. It is selected from any one of an alkyl group of 6, an aryl group of 6 to 12 carbon atoms, an alkoxyl group of 1 to 4 carbon atoms, and a hydroxy group.u is an integer of 0 to 5, but a compound having different u It may be a mixture.)

(Wherein, Ar ₃ is selected from any one kind of phenylene group, naphthylene group or biphenylene group. Ri and R j each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl having 6 to 12 carbon atoms It is selected from any one kind of an aryl group in which at least one of a group, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group and a cyanato group is substituted. Although it is shown, it may be a mixture of compounds different in 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（３）のＡｒ_２及び一般式（４）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（３）のＲｂ〜Ｒｇ及び一般式（４）のＲｉ、Ｒｊにおけるアルキル基及びアリール基は一般式（２）で記載したものと同様である。 Furthermore, as X in General Formula (2), the bivalent group represented by a following formula is mentioned.

(In the formula, z represents an integer of 4 to 7. R k independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Specific examples of Ar ₃ of Ar ₂ and of the general formula (3) (4), 1,4-phenylene group, a 1,3-phenylene group, 4,4'-biphenylene, 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 And 6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group and the like.
The alkyl group and the aryl group in Rb to Rg of General Formula (3) and Ri and Rj of General Formula (4) are the same as those described for General Formula (2).

Specific examples of the resin having in the molecule thereof an aromatic moiety substituted with at least one cyanato group represented by the general formula (2) include cyanatobenzene, 1-cyanato-2-1,1-cyanato-3-3 , Or 1-cyanato-4-methylbenzene, 1-cyanato-2-1, 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-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexyl ether Zen, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanide Anatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-triol Fluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-vinyl ester Cyanato-4-acetaminobenzene, 4-cyanatobenzopheno 1-Cyanato-2,6-di-tert-butylbenzene, 1,2-Dicyanatobenzene, 1,3-Dicyanatobenzene, 1,4-Dicyanatobenzene, 1,4-Dicyanato-2-tert -Butylbenzene, 1,4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-trimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3 -Dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 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-disocyanatocinaf Lene, 2,2- or 4,4-dicyanatobiphenyl, 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-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1 1-bis (4-cyanatophenyl) pentane, 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-dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-silane) Anatophenyl) 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) -2,2,3 4-trimethylpentane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1 Phenylethane, bis (4-cyanatophenyl) 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] bife Le, 4,4-dicyanatobenzophenone, 1,3-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, 3, 3-Bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthalein), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H)- On (cyanate of o-cresolphthalein), 9,9-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyana) To-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-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4-oxydiphthalic acid Imide, 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-cyano) Anatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1 -Methyl-3,3-bis (4-cyanatophenyl) indolin-2-one, 2-phenyl-3,3-bis (4-cyanatophenyl) yne Phosphorus-2-one, phenol novolak resin or cresol novolak resin (in a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol and formaldehyde compound such as formalin or paraformaldehyde are reacted in an acidic solution), Trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound and 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst Furan ring-containing phenol novolac resin (reaction of furfural with phenol in the presence of a basic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl tree , Binaphthol aralkyl resins, naphthol - a dihydroxynaphthalene aralkyl resin and a biphenyl aralkyl resin (a known method, Ar 3 _- (a CH 2 _Y) bishalogenomethyl compounds represented by ₂ and a phenol compound with an acidic catalyst or no catalyst Bis (alkoxymethyl) compounds represented by reaction or Ar _3- (CH ₂ OR) ₂ and bis (hydroxymethyl) compounds and phenol represented by Ar _3- (CH ₂ OH) ₂ A compound obtained by reacting the compound in the presence of an acidic catalyst, or a compound obtained by polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound), a phenol-modified xylene formaldehyde resin (a known method involves xylene formaldehyde resin and phenol The compound in the presence of an acidic catalyst (Reacted with), modified naphthalene formaldehyde resin (in which a naphthalene formaldehyde resin and a hydroxy substituted aromatic compound are reacted in the presence of an acidic catalyst by a known method), a phenol modified dicyclopentadiene resin, a polynaphthylene ether Phenolic resins such as phenolic resins having a structure (polyhydric hydroxynaphthalene compounds having two or more phenolic hydroxy groups in one molecule by dehydration according to a known method in the presence of a basic catalyst) are mentioned above. And the like, and prepolymers thereof, etc., but not limited thereto. These cyanate ester compounds can be used singly or in appropriate combination of two or more. A resin cured product using these cyanate ester compounds has excellent properties of high glass transition temperature, low thermal expansion and plating adhesion.

  Among these, phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, biphenylaralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, adamantane skeleton type cyanate ester Compounds are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred because they are excellent in flame retardancy, high in curability, and low in thermal expansion coefficient of the cured product.

Although content in the resin composition of this embodiment of a cyanate ester compound (A) can be suitably set according to the desired characteristic, it is not particularly limited, but 100 parts by mass of resin solid content in the resin composition 1 to 90 parts by mass is preferable.
Here, “resin solid content in the resin composition” refers to components excluding the solvent and the filler (C) in the resin composition, unless otherwise specified, and 100 parts by mass of resin solid content The total content of the solvent in the resin composition and the components excluding the filler (C) is 100 parts by mass.

The bismaleimide compound (B) used in the present invention is represented by the following formula (1).

The method for producing the compound of the formula (1) is not particularly limited, and may be produced by any method known as a maleimide compound synthesis method. As an example of such a preparation method, bismaleamic acid is synthesized by reaction with acid anhydride group of maleic anhydride and amino group of trimethylene bis (4-aminobenzoate), and then prepared by a known method of dehydrating cyclization. Methods etc. As a bismaleimide compound obtained in this manner, for example, bismaleimide, BMI-CUA-4 manufactured by KAI Co., Ltd. can be suitably used.

  The content of the bismaleimide compound (B) represented by the formula (1) in the resin composition of the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. When resin 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 is excellent in a glass transition temperature is obtained.

A filler (C) can also be used for the resin composition of this embodiment. A well-known thing can be used suitably as a filler (C) used for the resin composition of this embodiment, The kind is not specifically limited, The thing generally used in this field is used suitably. be able to. Specifically, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, silicas such as hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride , Nitrides such as carbon nitride and aluminum nitride, carbides such as silicon carbide, titanates such as strontium titanate and barium titanate, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, aluminum hydroxide, Aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated to reduce a part of crystal water), Metal hydroxide such as magnesium hydroxide and calcium hydroxide, Molybdenum compound such as molybdenum oxide and zinc molybdate , Calcium carbonate, magnesium carbonate, high Carbonates such as rotalcite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate etc., zinc stannate, alumina, gibbsite, boehmite, 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 G20, glass short fiber (E glass, T glass In addition to inorganic fillers such as D glass, S glass, Q glass etc., hollow glass, spherical glass, etc., rubber powder such as styrene type, butadiene type and acrylic type, core shell type Organic fillers such as rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder, etc. It is. These fillers can be used singly or in appropriate 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 are preferable. By using these fillers, properties such as thermal expansion properties, dimensional stability and flame retardancy of the resin composition are improved.

  Although content of the filler (C) in the resin composition of this embodiment can be suitably set according to the desired characteristic, it is not particularly limited, but the resin solid content in the resin composition was 100 parts by mass. In the case, 50 to 1600 parts by mass is preferable. By making content into 50 to 1600 mass parts, the moldability of a resin composition becomes favorable.

  In using an inorganic type filler (C) here, it is preferable to use a silane coupling agent and a wetting and dispersing agent together. As a silane coupling agent, what is generally used for the surface treatment of an inorganic substance can be used suitably, The kind in particular is not limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 -Epoxysilanes such as epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinylsilanes such as vinyl-tri (β-methoxyethoxy) silane, N-β- (N-vinylbenzylaminoethyl)- Cationic silanes such as γ-aminopropyltrimethoxysilane hydrochloride and phenylsilanes can be mentioned. The silane coupling agent can be used singly or in combination of two or more. Moreover, as a wetting and dispersing agent, what is generally used for paints can be used suitably, The kind in particular is not 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 Bick Chemie Japan Ltd. , BYK-W 940 and the like. The wetting and dispersing agents can be used alone or in combination of two or more.

Furthermore, in the resin composition of the present embodiment, a maleimide compound other than the bismaleimide compound represented by the formula (1) (hereinafter referred to as "other maleimide compound") as long as the desired properties are not impaired. The resin may contain an epoxy resin, a phenol resin, an oxacene 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.

  As the other maleimide compounds, generally known compounds can be used as long as they are maleimide compounds other than the bismaleimide compound represented by the formula (1) and which have one or more maleimide groups in one molecule. . For example, 4,4-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-) 4-maleimidophenyl) methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bis citraconic imide, m-phenylene bis citraconic imide, p-phenylene bis citraconic imide, 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, , 4-trimethyl) hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-Diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl-) 5-Methyl-4-citraconimidophenyl) methane, bis (3,5-diethyl-4-citraconimidophenyl) methane, polyphenylmethanemaleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds Etc. may be mentioned But the present invention is not particularly limited. These maleimide compounds can be used alone or in combination of two or more. Among these, novolak type maleimide compounds and biphenylaralkyl type maleimide compounds are particularly preferable.

  As an epoxy resin, if it is an epoxy resin which has 2 or more epoxy groups in 1 molecule, a well-known thing can be used suitably, The kind in particular is not limited. Specifically, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, aralkyl novolac Epoxy resin, biphenylaralkyl epoxy resin, naphthalene ether epoxy resin, cresol novolak epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified novolak epoxy resin, phenolaralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic type 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, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in view of flame retardancy and heat resistance. These epoxy resins can be used singly or in combination of two or more.

  As the phenolic resin, generally known ones can be used as long as they have two or more hydroxyl 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 phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type Phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin Alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a polymerizable unsaturated hydrocarbon of the group containing phenolic resin and hydroxyl-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenylaralkyl type phenol resins, naphtholaralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in view of flame retardancy. These phenol resins can be used singly or in combination of two or more.

  As the oxetane resin, those generally known can be used. For example, alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3, 3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane, 3, 3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyl oxetane, 3, 3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toho Gosei Co., Ltd.), OXT-121 (trade name of Toho Gosei Co., Ltd.), etc. There is no particular limitation, as mentioned. These oxetane resins can be used alone or in combination of two or more.

  As the benzoxazine compound, generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A-type benzoxazine BA-BXZ (trade name of Konishi Chemical) bisphenol F-type benzoxazine BF-BXZ (trade name of Konishi Chemical), bisphenol S-type benzooxazine BS-BXZ (trade name of Konishi Chemical), phenol Although there may be mentioned a phthalein type benzoxazine etc., it is not particularly limited. These benzoxazine compounds can be used alone or in combination of two or more.

  As compounds having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, (Meth) acrylates of monohydric or polyhydric alcohols 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) mare Although de resins, but it is not particularly limited. The compound which has these unsaturated groups can be used 1 type or in mixture of 2 or more types.

Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening speed 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 organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, phenol, xylenol, cresol, cresol, catechol, octylphenol, Phenolic compounds such as nonylphenol, alcohols such as 1-butanol, 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, and Derivatives such as carboxylic acids of dazoles or adducts of acid anhydrides thereof, 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 peroxy carbonate, di-2-ethylhexyl peroxy Peroxides such as carbonates, or azo compounds such as azobisisobutyronitrile can be mentioned. The curing accelerator can be used singly or in combination of two or more.
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, etc., and is not particularly limited. Usually, 100 parts by mass of resin solid content in the resin composition is used. When it is carried out, it is 0.005-10 mass parts.

  Furthermore, in the resin composition of the present embodiment, various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, elastomers, and flame retardant compounds as long as the desired properties are not impaired. And various additives may be used in combination. These are not particularly limited as long as they are generally used. For example, as flame retardant compounds, bromine compounds such as 4,4'-dibromobiphenyl, phosphate esters, melamine phosphates, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, silicone compounds Etc. In addition, as various additives, UV absorbers, antioxidants, photopolymerization initiators, fluorescent brightening agents, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, dispersions Agents, leveling agents, brighteners, polymerization inhibitors and the like. These can be used singly or in combination of two or more, as desired.

  In addition, the resin composition of this embodiment can use the 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 part, preferably all, of the various resin components described above is dissolved or compatible with the organic solvent. As the organic solvent, known solvents can be appropriately used so long as at least a part, preferably all of the various resin components described above can be dissolved or compatible, and the type 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, 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 singly or in combination of two or more.

  The resin composition of the present embodiment can be prepared according to a conventional method, and the cyanate ester compound (A), the bismaleimide compound (B) represented by the formula (1), and the other optional components described above are homogeneously used. The adjustment method is not particularly limited as long as the resin composition contained in is obtained. For example, the resin composition of the present embodiment can be easily prepared by sequentially blending the cyanate ester compound (A) and the bismaleimide compound (B) represented by the formula (1) in a solvent and stirring sufficiently. Can.

  In addition, at the time of preparation of a resin composition, the well-known process (stirring, mixing, kneading process, etc.) for dissolving or disperse | distributing each component uniformly 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-mentioned stirring, mixing, and kneading processing can be appropriately performed using, for example, a device intended for mixing such as a ball mill and a bead mill, or a known device such as a mixing device of revolution and rotation type.

The resin composition of the present embodiment can be used as an insulating layer of a printed wiring board or a material for a semiconductor package. For example, a solution obtained by dissolving the resin composition of the present invention in a solvent may be impregnated or coated on a substrate and dried to form a prepreg.
Moreover, it is possible to obtain a resin sheet by applying a solution obtained by dissolving the resin composition of the present invention in a solvent using a peelable plastic film as a support, and drying the solution. The resin sheet can be used as a buildup film or a dry film solder resist. Here, the solvent can be dried by heating at a temperature of 20 ° C. to 150 ° C. for 1 to 90 minutes. In addition, the resin composition can be used in an uncured state in which the solvent is dried only, or can be used in a semi-cured (B-staged) state as needed.

  Hereinafter, the prepreg of the present embodiment will be described in detail. The prepreg of the present embodiment is obtained by impregnating or applying the resin composition of the present embodiment described above to a substrate. The method for producing a prepreg is not particularly limited as long as it is a method for producing a prepreg by combining the resin composition of the present embodiment and a substrate. Specifically, after impregnating or applying the resin composition of the present embodiment to a substrate, the prepreg of the present embodiment is semicured by a method such as drying at 120 to 220 ° C. for about 2 to 15 minutes. It can be manufactured. At this time, the adhesion amount of the resin composition to the base material, that is, the resin composition amount (including the filler (C)) with respect to the total amount of the semi-cured prepreg 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, spherical glass etc., inorganic fibers other than glass such as quartz, organic substances such as polyimide, polyamide, polyester etc. Although textiles, such as textiles and liquid crystal polyester, are mentioned, it is not limited to these in particular. As the shape of the substrate, a woven fabric, a non-woven fabric, a roving, a chopped strand mat, a surfacing mat, etc. are known, but any may be used. A base material can be used individually by 1 type or in combination of 2 or more types. The thickness of the substrate is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminated plate applications, and in particular, the woven fabric which has been subjected to super-opening treatment or filling treatment has dimensional stability. From the point of view of Furthermore, a glass woven fabric surface-treated with a silane coupling agent such as epoxysilane treatment and aminosilane treatment is preferable from the viewpoint of moisture resistance and heat resistance. In addition, a liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics.

Further, the metal foil-clad laminate of the present embodiment is obtained by laminating at least one or more of the above-described prepregs, arranging metal foils on one side or both sides, and laminating and forming them. Specifically, it can be produced by laminating one or a plurality of the above-described prepregs, arranging a metal foil such as copper or aluminum on one side or both sides, and laminating and forming the same. The metal foil used here is not particularly limited as long as it is used for a printed wiring board material, but a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. Moreover, the thickness of metal foil is although it does not specifically limit, 2-70 micrometers is preferable and 3-35 micrometers is more preferable. As a molding condition, the method of the common laminated board for printed wiring boards and a multilayer board is applicable. For example, by using a multi-stage press, multi-stage vacuum press, continuous forming machine, autoclave forming machine, etc., laminating and forming 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. A multilayer board can also be obtained by laminating and molding the above-described prepreg and a wiring board for the inner layer separately prepared. As a method of manufacturing a multilayer board, for example, copper foils of 35 μm are disposed on both sides of one of the prepregs described above, and laminated under the above conditions, an inner layer circuit is formed, and the circuit is blackened. The inner layer circuit board is formed, and then the inner layer circuit board and the above-mentioned prepreg are alternately arranged one by one, and a copper foil is further arranged in the outermost layer, preferably laminated under a vacuum under the above conditions By doing this, a multilayer board can be produced.

  And the metal foil tension laminate 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 above-mentioned copper-clad laminate, is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is produced. The inner layer circuit surface of the inner layer substrate is optionally subjected to a surface treatment to increase the adhesive strength, and then the required number of prepregs described above are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is laminated on the outer side. Heat and pressure to form a single piece. In this manner, a multilayer laminate is produced in which an insulating layer made of a cured product of a base material and a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Then, after drilling processing for through holes and via holes in this multilayer laminate, a plated metal film is formed on the wall surface of this hole to make the inner layer circuit and the metal layer outer layer circuit conductive, and further the outer layer circuit The printed wiring board is manufactured by etching the metal foil for forming the outer layer circuit.

  The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. That is, the prepreg (the base material and the resin composition of the present embodiment impregnated or coated with the same) of the above-described embodiment, the layer of the resin composition of the metal foil-clad laminate of the above-described embodiment The layer consisting of a resin composition will be comprised from the insulating layer containing the resin composition of this embodiment.

  On the other hand, the resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the resin composition of the above present embodiment in a solvent on a support and drying. As a support body used here, for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, a release film in which a release agent is coated on the surface of these films, polyimide An organic film substrate such as a film, a conductor foil such as copper foil or aluminum foil, a glass plate, a SUS plate, a plate such as FRP, etc. may be mentioned, but it is not particularly limited. As a coating method, for example, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a support by a bar coater, a die coater, a doctor blade, a baker applicator or the like to form a support and a resin sheet. The method of producing the integral lamination sheet is mentioned. In addition, after drying, the support may be peeled or etched from the laminated sheet to form a single-layer sheet that is a single resin sheet. In addition, using a support by forming in a sheet shape by supplying a solution obtained by dissolving the resin composition of the present embodiment in the above-described embodiment in a solvent into a mold having a sheet-like cavity and drying. It is also possible to obtain a single layer sheet.

  In the preparation 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. Since the curing of the resin composition proceeds if any, temperatures of 20 ° C. to 200 ° C. for 1 to 90 minutes are preferable. In addition, 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 solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited. The thickness of the coating is preferably 0.1 to 500 μm because the solvent tends to remain at the time of drying when the coating thickness becomes large.

  EXAMPLES The present invention will be described in more detail by way of synthesis examples, examples and comparative examples, although the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Cyanate Ester Compound 300 g (1.28 mol in terms of OH group) of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (per 1 mol of hydroxy group) 1.5 mol) was dissolved in 1800 g of dichloromethane, which was referred to as solution 1.
125.9 g (2.05 mol) of cyanogen chloride (1.6 mol to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol to 1 mol of hydroxy group) The solution 1 was poured over 30 minutes, keeping 1205.9 g of water under stirring, at a solution temperature of -2 to -0.5 ° C. After completion of 1 injection of solution, after stirring for 30 minutes at the same temperature, 10 minutes of a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol per 1 hydroxyl group) is dissolved in dichloromethane I poured it over. After completion of solution 2 injection, the reaction was completed by stirring for 30 minutes at the same temperature.
Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed five times with 1300 g of water. The electric conductivity of the fifth washing with water was 5 μS / cm, and it was confirmed that washing with water sufficiently removed the removable ionic compound.
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 material). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed an absorption of 2250 cm ⁻¹ (cyanate group) and no absorption of a hydroxy group.

Example 1
50 parts by mass of SNCN obtained by Synthesis Example 1, 50 parts by mass of a bismaleimide compound represented by the formula (1) (BMI-CUA-4, manufactured by KAI / AI Kasei Co., Ltd.), fused silica (SC2050 MB, manufactured by Admatex Co., Ltd.) 100 parts by mass and 0.15 parts by mass of zinc octylate (manufactured by Nippon Chemical Industrial Co., Ltd.) were mixed to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and coated on an E glass woven fabric having a thickness of 0.1 mm, and dried by heating at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 50% by mass.

Four sheets of the obtained prepregs, eight sheets are stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Metals Co., Ltd.) is disposed at the top and bottom, and the pressure is 30 kgf / cm ² and temperature is 220 ° C. for 120 minutes. The laminate molding of the above was performed to obtain a metal foil-clad laminate having an insulating layer thickness of 0.4 and 0.8 mm. The glass transition temperature (Tg), moisture absorption heat resistance, copper foil peel strength, plating peel strength, thermal expansion coefficient, and solder heat resistance were evaluated using the obtained metal foil tension laminate sheet. The results are shown in Table 1.

(Comparative example 1)
In Example 1, instead of using 50 parts by mass of the bismaleimide compound represented by the formula (1), 50 parts by mass of novolac maleimide (BMI-70, manufactured by Kai-I Kasei Co., Ltd.) and 0. 1 part of zinc octylate are used. A metal foil-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1 except that 22 parts by mass was used. The evaluation results of the obtained metal foil-clad laminate are shown in Table 1.

(Measurement method and evaluation method)
Glass transition temperature: The obtained eight metal foil-clad laminates were measured for glass transition temperature by a dynamic viscosity analyzer (manufactured by TA Instruments) according to JIS C6481 by a DMA method.
Hygroscopic heat resistance: A pressure cooker tester (PC manufactured by Hirayama Seisakusho, Ltd.) obtained by etching and removing all the copper foils other than the half of one side of the 50 mm × 50 mm sample obtained by laminating four metal foil-clad laminates. The appearance change after being immersed in a solder at 260 ° C. for 60 seconds was visually observed after treatment at 121 ° C. and 2 atm for 5 hours in type 3). (Number of blister occurrences / number of tests)
Copper foil peel strength: About the obtained eight metal foil clad laminate, using a test piece (30 mm × 150 mm × 0.8 mm) with a 12 μm metal foil according to JIS C6481 The peel strength of was measured, and the average value of the lower limit was taken as the measured value.
Plating peel strength: The obtained eight-layered metal foil clad laminate was subjected to an electroless copper plating process (used chemical name: MCD-PL, MDP-2, MAT-SP, MAB-4-C, manufactured by Uemura Kogyo Co., Ltd.) About 0.8 micrometer electroless copper plating was given by MEL-3-APEA ver. 2), and 1 hour drying was performed at 130 degreeC. Subsequently, electrolytic copper plating was applied such that the thickness of the plated copper became 18 μm, and drying was performed at 180 ° C. for one hour. Thus, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was produced and evaluated. The adhesion of the plated copper was measured three times according to JIS C6481, and the average value was determined.
Thermal expansion coefficient: The thermal expansion coefficient of the glass cloth in the longitudinal direction of the insulating layer of the laminate obtained by the TMA method (Thermo-mechanical analysis) specified in Jl S C 6481 with respect to the obtained eight metal foil clad laminate Was measured and its value was determined. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, the thermal mechanical analyzer (manufactured by TA Instruments) at 40 ° C. to 340 ° C. at 10 ° C./min. The temperature was raised, and the linear thermal expansion coefficient (ppm / ° C.) at 60 ° C. to 120 ° C. was measured.
Solder heat resistance (solder float): The obtained four-ply metal foil-clad laminate, 50 × 50 mm sample was floated in 280 ° C. solder for 30 minutes, and the presence or absence of appearance abnormality was visually determined. (Number of occurrence of delamination / number of tests)

  As apparent from Table 1, it was confirmed that a prepreg, a printed wiring board and the like excellent in heat resistance, peel strength and thermal expansion coefficient can be realized by using the resin composition of the present invention.

As described above, the resin composition of the present invention can be used, for example, in electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminate materials, in various applications such as electric and electronic materials, machine tool materials, aviation materials, etc. Widely and effectively usable as resists, buildup laminate materials, etc. Especially, particularly effective as printed wiring board materials compatible with high integration and high density in recent information terminal equipment and communication equipment etc. It is. Moreover, since the laminates and metal foil-clad laminates of the present invention have excellent heat resistance, peel strength, and thermal expansion coefficient, their industrial practicability is extremely high.

Claims (9)

A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).

  The resin composition according to claim 1, wherein the content of the bismaleimide compound (B) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass.   Furthermore, the resin composition of Claim 1 or 2 containing a filler (C).   Furthermore, among the group selected from maleimide compounds other than the bismaleimide compound (B) represented by the formula (1), epoxy resins, phenol resins, oxacene resins, benzoxazine compounds, compounds having a polymerizable unsaturated group The resin composition as described in any one of Claims 1-3 containing any 1 or more types.   The resin composition according to claim 3 or 4, wherein the content of the filler (C) in the resin composition is 50 to 1600 parts by mass, when the resin solid content in the resin composition is 100 parts by mass. object.   The prepreg formed by impregnating or apply | coating the resin composition as described in any one of Claims 1-5 to a base material.   A metal foil-clad laminate obtained by laminating at least one or more sheets of the prepreg according to claim 6, and laminating and forming a metal foil on one side or both sides thereof.   The resin sheet formed by apply | coating and drying the resin composition as described in any one of Claims 1-5 on the surface of a support body. It is a printed wiring board containing an insulating layer and a conductor layer formed in the surface of the insulating layer, and the insulating layer is a printed wiring containing the resin composition according to any one of claims 1 to 5. Board.