JP2017165827A - 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 that can be cured to form a cured product which has high glass-transition temperature and low water absorption and can realize a printed wiring board excellent in moisture-absorbing heat resistance and adhesion to metal.SOLUTION: The resin composition contains: a compound (A) having, in the main chain, bisbenzoxazine connected by an organic group represented by a specific general formula; a cyanic acid ester compound (B); and a maleimide compound (C).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 are known as resins for printed wiring boards having excellent heat resistance and electrical characteristics, and resin compositions using bisphenol A type cyanate ester compounds and other thermosetting resins are known. Widely used for printed wiring board materials. Bisphenol A type cyanate ester compound has excellent electrical properties, mechanical properties, chemical resistance, etc., but is insufficient in low water absorption, moisture absorption heat resistance, flame resistance, and heat resistance Therefore, studies have been made on cyanate ester compounds for the purpose of further improving the properties.
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.

  In Patent Document 1, a novolak cyanate ester compound has been proposed as a resin having a structure different from that of the bisphenol A type cyanate ester compound. However, the novolac cyanate ester compound tends to be insufficiently cured, and the obtained curing is obtained. There was a problem that the water absorption rate of the product was large and the moisture absorption heat resistance was lowered. As a method for solving these problems, Patent Document 2 proposes prepolymerization of a novolac-type cyanate ester compound and a bisphenol A-type cyanate ester compound, but the curability is improved by prepolymerization. However, since improvement in the properties of low water absorption, moisture absorption heat resistance, and heat resistance is still insufficient, further improvements in water absorption and heat resistance are required.

Japanese Patent Laid-Open No. 11-124433 JP 2000-191776 A

  The present invention aims to provide a resin composition capable of realizing a printed wiring board having a high glass transition temperature and low water absorption, and excellent in moisture absorption heat resistance and adhesion to metal. An object of the present invention is to provide a prepreg and a single layer or laminated 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 contain a benzoxazine compound (A), a cyanate ester compound (B), and a maleimide compound (C) having a structure represented by the following general formula (1). It has been found that by using a resin composition, a cured product having a high glass transition temperature, excellent low water absorption, moisture absorption heat resistance and metal adhesion can be obtained, and the present invention has been achieved. That is, the present invention is as follows.

（式中、Ｒ１及びＲ２は、各々独立して、炭素数１〜２０の有機基を表し、ｐは、ベンゼン環に結合する有機基Ｒ１の数を表し、０〜３の整数である。ｑは、ベンゼン環に結合する有機基Ｒ２の数を表し、０〜３の整数である。Ｘは、炭素数１〜２０の、ヘテロ元素を含んでいてもよい、直鎖、分岐、若しくは環状の構造を持つ脂肪族の有機基、又は芳香族の有機基を表し、Ｙは各々独立に、炭素数１〜２０の、ヘテロ元素を含んでいてもよい、直鎖、分岐、若しくは環状の構造を持つ脂肪族の有機基、芳香族の有機基又は単結合を表し、Ｚは各々独立に、下記式（２ａ）から（２ｃ）で表される群より選択される１つを表し、ｎは、１〜５００の整数を表す。）

（式中、Ｒ３は、炭素数１〜２０の有機基を表す。ｒはベンゼン環に結合する有機基の数を表し、０〜４の整数である。＊は式（１）におけるＹとの結合部位を表す。） 1. A resin composition comprising a benzoxazine compound (A), a cyanate ester compound (B) and a maleimide compound (C) having a structure represented by the general formula (1).

(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 20 carbon atoms, p represents the number of organic groups R 1 bonded to the benzene ring, and is an integer of 0 to 3. q Represents the number of organic groups R2 bonded to the benzene ring and is an integer of 0 to 3. X is a linear, branched, or cyclic group having 1 to 20 carbon atoms, which may contain a hetero element. Represents an aliphatic organic group having a structure or an aromatic organic group, and each Y independently represents a linear, branched, or cyclic structure having 1 to 20 carbon atoms and optionally containing a heteroelement. Each represents an aliphatic organic group, an aromatic organic group, or a single bond, and each Z independently represents one selected from the group represented by the following formulas (2a) to (2c), and n is Represents an integer of 1 to 500.)

(In the formula, R3 represents an organic group having 1 to 20 carbon atoms. R represents the number of organic groups bonded to the benzene ring, and is an integer of 0 to 4. * represents Y in Formula (1). Represents the binding site.)

  2. 1. X in the general formula (1) is an organic group having 1 to 3 carbon atoms. The resin composition described in 1.

（式中、＊は式（１）におけるＹとの結合部位を表す。） 3. Y in the general formula (1) is any structure or single bond selected from the group represented by the following formula: Or 2. The resin composition described in 1.

(In the formula, * represents a binding site with Y in formula (1).)

  4). Content in the resin composition of the said benzoxazine compound (A) is 1-25 mass parts with respect to 100 mass parts of resin solid content. ~ 3. The resin composition as described in any one of these.

  5. Furthermore, containing a filler (D). ~ 4. The resin composition as described in any one of these.

  6). 4. Content of the filler (D) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content. The resin composition described in 1.

  7). Furthermore, any of the groups selected from epoxy resins, phenol resins, oxetane resins, compounds having polymerizable unsaturated groups, and benzoxazine compounds other than the benzoxazine compound (A) represented by the general formula (1) Containing one or more kinds. ~ 6. The resin composition as described in any one of these.

  8). 1. a substrate and impregnated or coated on the substrate; ~ 7. A prepreg having the resin composition according to any one of the above.

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

  10. 1. disposed on the support and the surface of the support; ~ 7. The resin sheet which has the resin composition as described in any one of these.

  11. An insulating layer; and a conductor layer formed on the surface of the insulating layer. ~ 7. The printed wiring board containing the resin composition as described in any one of these.

  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.

（式中、Ｒ１及びＲ２は、各々独立して、炭素数１〜２０の有機基を表し、ｐは、ベンゼン環に結合する有機基Ｒ１の数を表し、０〜３の整数である。ｑは、ベンゼン環に結合する有機基Ｒ２の数を表し、０〜３の整数である。Ｘは炭素数１〜２０の、ヘテロ元素を含んでいてもよい、直鎖、分岐、若しくは環状の構造を持つ脂肪族の有機基又は芳香族の有機基を表し、Ｙは各々独立に、炭素数１〜２０の、ヘテロ元素を含んでいてもよい、直鎖、分岐、若しくは環状の構造を持つ脂肪族の有機基、芳香族のジアミン残基を有する有機基又は単結合を表し、Ｚは各々独立に、下記式で表される群より選択される１つを表し、ｎは、１〜５００の整数を表す。）

（式中、Ｒ３は、炭素数１〜２０の有機基を表す。ｒはベンゼン環に結合する有機基の数を表し、０〜４の整数である。＊は式（１）におけるＹとの結合部位を表す。） The benzoxazine compound (A) used in the present embodiment has a structure represented by the general formula (1).

(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 20 carbon atoms, p represents the number of organic groups R 1 bonded to the benzene ring, and is an integer of 0 to 3. q Represents the number of organic groups R2 bonded to the benzene ring, and is an integer of 0 to 3. X is a linear, branched or cyclic structure having 1 to 20 carbon atoms and optionally containing a hetero element. Represents an aliphatic organic group or an aromatic organic group, and each Y independently represents a fatty acid having a linear, branched, or cyclic structure, which may contain a heteroelement having 1 to 20 carbon atoms. An organic group having an aromatic group, an organic group having an aromatic diamine residue, or a single bond, each Z independently represents one selected from the group represented by the following formula, and n is 1 to 500 Represents an integer.)

(In the formula, R3 represents an organic group having 1 to 20 carbon atoms. R represents the number of organic groups bonded to the benzene ring, and is an integer of 0 to 4. * represents Y in Formula (1). Represents the binding site.)

X in the formula of the benzoxazine compound (A) used in the present embodiment is more preferably an organic group having 1 to 3 carbon atoms, and is an isopropylidene group (—C (CH ₃ ) ₂ —). Is more preferable.

Y in the formula of the benzoxazine compound (A) used in the present embodiment is preferably any structure or single bond selected from the group represented by the following formulas (3a) to (3h).

（式中、Ｒ４は、炭素数１〜２０の有機基を表す。ｓはベンゼン環に結合する有機基の数を表し、０〜４の整数である。） The resin cured product using the benzoxazine compound having such a structure realizes a high glass transition temperature, excellent low water absorption and moisture absorption heat resistance, and further improves metal adhesion. Among these, a benzoxazine compound (A) having a structure represented by the following formulas (4a) to (4c) is particularly preferable from the viewpoint of improving the above characteristics.

(In the formula, R4 represents an organic group having 1 to 20 carbon atoms. S represents the number of organic groups bonded to the benzene ring, and is an integer of 0 to 4.)

（式中、Ｒ５は、炭素数１〜４の有機基を表す。ｔはベンゼン環に結合する有機基の数を表し、０又は１の整数である。） The method for obtaining the benzoxazine compound (A) used in the present embodiment is not particularly limited. Moreover, such a benzoxazine compound (A) can also be obtained as a commercial product, for example, DIC Corporation containing at least one of the groups represented by the following formulas (5a) to (5c) A manufactured benzoxazine compound, EXS-Z-1, can be preferably used.

(In the formula, R5 represents an organic group having 1 to 4 carbon atoms. T represents the number of organic groups bonded to the benzene ring, and is an integer of 0 or 1.)

The content of the benzoxazine compound (A) thus obtained 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, 1-25 mass parts is preferable, More preferably, it is 1-20 mass parts, More preferably, it is 1-15 mass parts.
Here, unless otherwise specified, “resin solid content in the resin composition” refers to a component in the resin composition excluding the solvent and filler (D), and the resin solid content of 100 parts by mass is The total of the components excluding the solvent and filler in the resin composition is 100 parts by mass.

（式中、Ａｒ_１は、ベンゼン環、ナフタレン環又は２つのベンゼン環が単結合したものを示し、複数ある場合は互いに同一であっても異なっていても良い。Ｒａ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Ｒａにおける芳香環は置換基を有していてもよく、Ａｒ_１及びＲａにおける置換基は任意の位置を選択できる。ｕはＡｒ_１に結合するシアナト基の数を示し、各々独立に１〜３の整数である。ｖはＡｒ_１に結合するＲａの数を示し、Ａｒ_１がベンゼン環の時は４−ｕ、ナフタレン環の時は６−ｕ、２つのベンゼン環が単結合したものの時は８−ｕである。ｗは平均繰り返し数を示し、０〜５０の整数であり、シアン酸エステル化合物は、ｗが異なる化合物の混合物であってもよい。Ｗは、複数ある場合は各々独立に、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（例えば−Ｎ−Ｒ−Ｎ−など（ここでＲは有機基を示す。））、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−）、２価の硫黄原子又は２価の酸素原子のいずれかを示す。） The cyanate ester compound (B) used in the present embodiment is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanate group in the molecule. As a cyanate ester compound,
For example, what is represented by General formula (6) is mentioned.

(In the formula, Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings, and when there are a plurality of them, they may be the same or different. Ra is independently a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms in the bond Ra The aromatic ring may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position, and u represents the number of cyanato groups bonded to Ar ₁ , each independently an integer of 1 to 3. V represents the number of Ra bonded to Ar ₁ , and when Ar ₁ is a benzene ring, 4-u, when Na ₁ is a naphthalene ring, 6-u, and when two benzene rings are a single bond, 8- u is the average number of repetitions, 0 to 5 The cyanate ester compound may be a mixture of compounds having different w. When there are a plurality of W, each independently represents a single bond or a divalent organic group having 1 to 50 carbon atoms (hydrogen An atom may be substituted with a hetero atom), a divalent organic group having 1 to 10 nitrogen atoms (for example, —N—R—N— and the like (where R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group (—OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom or 2 Any one of valent oxygen atoms.)

The alkyl group in Ra in the general formula (6) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).
In addition, the hydrogen atom in the alkyl group in the general formula (6) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. Also good.

  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, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.

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, trifluorophenyl. Groups, methoxyphenyl groups, and o-, m- or p-tolyl groups. Furthermore, examples of the alkoxy 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 having 1 to 50 carbon atoms in W of the general formula (6) include alkylene groups such as methylene group, ethylene group, trimethylene group and propylene group, cyclopentylene group, cyclohexylene group, Examples thereof include divalent organic groups having an aromatic ring such as a cycloalkylene group such as a trimethylcyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-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 a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in W of the general formula (6) include a group represented by —N—R—N—, an imino group, and a polyimide group.

ここで、式中、Ａｒ_２はベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基のを示し、ｘが２以上の場合、互いに同一であっても異なっていてもよい。Ｒｂ、Ｒｃ、Ｒｆ、及び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、又はフェノール性ヒドロキシ基を少なくとも１個有するアリール基示す。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のアルコキシ基及びヒドロキシ基を示す。ｘは０〜５の整数を示す。

ここで、式中、Ａｒ_３はベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基を示し、ｙが２以上の場合、互いに同一であっても異なっていてもよい。Ｒｉ、及び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のアルコキシ基、ヒドロキシ基、トリフルオロメチル基、又はシアナト基が少なくとも１個置換されたアリール基を示す。ｙは０〜５の整数を示すが、ｙが異なる化合物の混合物であってもよい。 Moreover, as an organic group of W in General formula (6), what is a structure represented by following General formula (7) or following General formula (8) is mentioned.

Here, in the formula, Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group, or a biphenyltetrayl group, and when x is 2 or more, they may be the same as or different from each other. Rb, Rc, Rf, and Rg are each independently an aryl group having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Show. Rd and Re each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxy group. x shows the integer of 0-5.

Here, in the formula, Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group, or a biphenyltetrayl group, and when y is 2 or more, they may be the same as or different from each other. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group substituted with at least one cyanato group. y represents an integer of 0 to 5, but may be a mixture of compounds having different y.

ここで式中、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のアルキル基を示す。 Furthermore, as W in General formula (6), the bivalent group represented by a following formula is mentioned.

Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar _{2 in the} general formula (7) and Ar _{3 in} the general formula (8) include two carbon atoms represented by the general formula (7) or two oxygen atoms represented by the general formula (8). A benzenetetrayl group bonded to the 1,4-position or the 1,3-position, the two carbon atoms or the two oxygen atoms are in the 4,4′-position, 2,4′-position, 2,2′-position, The biphenyltetrayl group bonded to the 2,3′-position, 3,3′-position, or 3,4′-position, and the two carbon atoms or the two oxygen atoms are in the 2,6-position, 1,5 Naphthalenetetrayl group bonded to the 1-position, 1,6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.
Rb, Rc, Rd, Re, Rf, and Rg in the general formula (7) and the alkyl group and aryl group in Ri and Rj in the general formula (8) have the same meanings as those in the general formula (6).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (6) 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-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenze 1-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- Cyanatobenzophenone, 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-dimethylbenzene, 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-dicyanatosinaphthalene, 2,2'- or 4,4'- Dicyanato Biphenyl, 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) pe Tan, 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-cyanatophenyl) octane, 3,3-bis (4-cyanatopheny ) -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 -Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenylethane Bis (4-cyanato Phenyl) 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-dicyanatobenzopheno 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, 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 (o-cresolphthalein Nate), 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 -Triazine, 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-si Anatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanato) Eniru) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one. Other specific examples of the compound represented by the general formula (6) include phenol novolak resins and cresol novolak resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc. by a known method). Of formaldehyde compound in an acidic solution), trisphenol novolak resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9,9-). Bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), furan ring-containing phenol novolac resin (furfural and phenol in the presence of a basic catalyst), phenol aralkyl resin, The Tetrazole aralkyl resin, naphthol aralkyl resin, a binaphthol aralkyl resin and a biphenyl aralkyl resin (a known _{method, Ar 2 -. (CH 2} Y) 2 (Ar 2 represents a phenyl group, Y represents a halogen atom or less, this paragraph The same as in the above)) and a bis (alkoxymethyl) compound represented by Ar _2- (CH ₂ OR) ₂ obtained by reacting a bishalogenomethyl compound and a phenol compound with an acidic catalyst or non-catalyst. A compound, a bis (hydroxymethyl) compound represented by Ar ₂ — (CH ₂ OH) ₂ and a phenol compound reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound And phenol-modified xylene formaldehyde Resin (reacted xylene formaldehyde resin and phenol compound in the presence of an acidic catalyst by a known method), modified naphthalene formaldehyde resin (naphthalene formaldehyde resin and hydroxy-substituted aromatic compound by an acid catalyst by a known method) A phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure (a polyvalent hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule by a known method) And those obtained by cyanating a phenol resin such as those obtained by dehydration condensation in the presence of a basic catalyst by the same method as described above, and these prepolymers. These are not particularly limited. These cyanate ester compounds can be used singly or in appropriate combination of two or more.

  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 Compounds are preferred, and naphthol aralkyl cyanate compounds are particularly preferred.

  The cured resin using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

  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.

（式中、Ｒｍは、各々独立に水素原子又はメチル基を示し、ｎは、１以上の整数を示す。）
マレイミド化合物の本実施形態の樹脂組成物における含有量は、所望する特性に応じて適宜設定することができ、特に限定されないが、樹脂組成物中の樹脂固形分を１００質量部とした場合、１〜９０質量部が好ましい。含有量が１〜９０質量部の範囲である場合、ガラス転移温度に優れる樹脂組成物が得られる。 As the maleimide compound (C) 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, novolac maleimide, biphenylaralkyl maleimide, represented by the following formula (9) Maleimide compounds, and of 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 two or more. Among these, a novolac maleimide compound, a biphenyl aralkyl maleimide compound, and a maleimide compound represented by the following formula (9) are particularly preferable.

(In the formula, each Rm independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)
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 (D) 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.

  The content of the filler (D) 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. When the content of the filler (D) is within the above range, the moldability of the resin composition becomes good, and the cured product of the resin composition containing the filler (D) has flame retardancy, heat resistance and It tends to be more excellent in moisture absorption heat resistance.

  Here, in using the filler (D), 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, the resin composition of the present embodiment is represented by an epoxy resin, a phenol resin, an oxetane resin, a compound having a polymerizable unsaturated group, and the general formula (1) as long as desired characteristics are not impaired. One or more selected from the group consisting of benzoxazine compounds other than benzoxazine compounds (hereinafter referred to as “other benzoxazine compounds”) may be contained.

  As an epoxy resin, if it is an epoxy resin which has two or more epoxy groups in 1 molecule, a well-known thing can be used suitably, The kind is not specifically 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.

  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.) Although it is mentioned, it is not particularly limited. These oxetane resins can be used singly or in combination of two or more.

  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 Although de resins, but it is not particularly limited. These compounds having an unsaturated group can be used singly or in combination of two or more.

  As other benzoxazine compounds, those having a unit represented by the general formula (1) and those having at least one dihydrobenzoxazine ring in one molecule should be used. Can do. 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), P -D type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Fa type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be mentioned. These benzoxazine compounds can be used alone or in combination of two or more.

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, etc., and is not particularly limited, but is usually based on 100 parts by mass of resin solids in the resin composition. 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 this embodiment can be used as an aspect (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible in 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 includes a benzoxazine compound (A), a cyanate ester compound (B), and a maleimide compound (C) having a structure represented by the general formula (1). ), The preparation method is not particularly limited as long as it is a method by which a resin composition containing the other optional components described above can be obtained uniformly. For example, the benzoxazine compound (A), the cyanate ester compound (B), and the maleimide compound (C) having a structure represented by the general formula (1) are sequentially blended in a solvent, and this embodiment is sufficiently stirred. The resin composition can be easily prepared.

  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 (D), 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 embodiment 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 (D)) 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 this embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent is likely to remain in the resin composition at a low temperature, and the temperature is high. 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.

Example 1
Benzoxazine compound (EXS-Z-1, manufactured by DIC Corporation) containing at least one of the groups represented by the general formulas (5a) to (5c), 7.5 parts by mass, 2,2-bis Prepolymer of (4-cyanatephenyl) propane (CA210, cyanate equivalent 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 60.5 parts by mass, maleimide compound represented by formula (10) (BMI-2300, maleimide equivalent 275 g / eq. 32 parts by mass of Daiwa Kasei Co., Ltd., 100 parts by mass of fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.), 0.06 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) A varnish was obtained. 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%.

Four or eight of the obtained prepregs are stacked, and a 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) is placed up and down, and the pressure is 30 kgf / cm ² and the temperature is 230 ° C. for 120 minutes. Then, a metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained. Using the obtained metal foil-clad laminate, glass transition temperature, water absorption, moisture absorption heat resistance and plating peel strength were evaluated. The results are shown in Table 1.

(Measurement method and evaluation method)
[Glass-transition temperature]
With respect to the obtained metal foil-clad laminate with an insulating layer thickness of 0.8 mm, the glass transition temperature was measured by the DMA method using a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481.
[Water absorption rate]
Using the obtained metal foil-clad laminate with a thickness of 0.8 mm and a sample of 30 mm × 30 mm, in accordance with JIS C6481, 121 ° C. with a pressure cooker tester (Hirayama Seisakusho, PC-3 type) The water absorption after 5 hours treatment at 2 atmospheres was measured.
[Hygroscopic heat resistance]
A test piece obtained by etching away all the copper foil other than half of one side of the obtained metal foil-clad laminate having a thickness of 0.4 mm and a 50 mm × 50 mm sample was subjected to a pressure cooker tester (made by Hirayama Seisakusho, PC- Type 3) was treated at 121 ° C. and 2 atm for 5 hours, and then visually observed for appearance abnormality after being immersed in 260 ° C. solder for 60 seconds. (Number of swelling / number of tests)
[Plating peel strength]
With respect to the obtained metal foil-clad laminate having an insulating layer thickness of 0.8 mm, the electrolytic copper foil was removed by etching, and a swelling treatment solution (OPC-B103 pre-etched 400 ml / L, sodium hydroxide 13 g / L manufactured by Okuno Pharmaceutical Co., Ltd.) ) For 5 minutes at 65 ° C. Next, it was immersed for 8 minutes at 80 ° C. in a roughening treatment solution (OPC-1540MN 100 ml / L, OPC-1200 Epochetch 100 ml / L) manufactured by Okuno Pharmaceutical. Finally, desmear treatment was performed in a neutralization treatment solution (OPC-1300 Neutrizer 200 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd. for 5 minutes at 45 ° C. Thereafter, in an electroless copper plating process manufactured by Okuno Pharmaceutical Co., Ltd. (chemical names used: OPC-370 Condy Clean M, OPC-SAL M, OPC-80 Catalyst, OPC-555 Accelerator M, ATS Ad Copper IW) About 0.5 μm of electroless copper plating was applied, followed by drying at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm (30 mm × 150 mm × 0.8 mm), and drying was performed at 180 ° C. for 1 hour. Thus, a circuit wiring board sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was produced. Using the circuit wiring board sample, the adhesive strength of the plated copper was measured according to JIS C6481, the peel strength was measured with a test number of 3, and the average of the lower limit values was taken as the measured value. When peeling occurred at the interface between the insulating layer and the conductor layer (plated copper) of the manufactured sample and the plating peel strength could not be measured, the determination was “not measurable”.

(Example 2)
In Example 1, except that 15 parts by mass of benzoxazine compound EXS-Z-1, 55.6 parts by mass of CA210, 29.4 parts by mass of BMI-2300, and 0.04 parts by mass of zinc octylate were used. In the same manner as in Example 1, a metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Comparative Example 1)
In Example 1, except that the benzoxazine compound EXS-Z-1 was not used, 65.4 parts by mass of CA210, 34.6 parts by mass of BMI-2300, and 0.1 parts by mass of zinc octylate were used. In the same manner as in Example 1, a metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Comparative Example 2)
6. In Example 1, instead of using 7.5 parts by mass of the benzoxazine compound EXS-Z-1, a Pd-type benzoxazine compound (manufactured by Shikoku Chemicals Co., Ltd.) represented by the formula (11) A metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained in the same manner as in Example 1 except that 5 parts by mass was used. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Comparative Example 3)
In Example 1, instead of using 7.5 parts by mass of the benzoxazine compound EXS-Z-1, an Fa type benzoxazine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd.) represented by the formula (12) 7. A metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained in the same manner as in Example 1 except that 5 parts by mass was used. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Comparative Example 4)
In Example 2, instead of using 15 parts by mass of the benzoxazine compound EXS-Z-1, 15 parts by mass of a Pd-type benzoxazine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd.) represented by the formula (11), A metal foil-clad laminate having an insulating layer thickness of 0.4 mm and 0.8 mm was obtained in the same manner as in Example 2 except that 0.05 part by mass of zinc octylate was used. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

  As is apparent from Table 1, by using the resin composition of the present invention, a prepreg, printed wiring board, etc. having high glass transition temperature and low water absorption, excellent moisture absorption heat resistance and adhesion to metal, etc. 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., for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminated materials, 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, the laminates and metal foil-clad laminates of the present invention not only have a high glass transition temperature and low water absorption, but also have excellent performance in moisture absorption heat resistance and adhesion to metals. The practical utility is extremely high.

Claims (11)

The resin composition containing the benzoxazine compound (A) which has a structure represented by General formula (1), a cyanate ester compound (B), and a maleimide compound (C).

(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 20 carbon atoms, p represents the number of organic groups R 1 bonded to the benzene ring, and is an integer of 0 to 3. q Represents the number of organic groups R2 bonded to the benzene ring and is an integer of 0 to 3. X is a linear, branched, or cyclic group having 1 to 20 carbon atoms, which may contain a hetero element. Represents an aliphatic organic group having a structure or an aromatic organic group, and each Y independently represents a linear, branched, or cyclic structure having 1 to 20 carbon atoms and optionally containing a heteroelement. Each represents an aliphatic organic group, an aromatic organic group, or a single bond, and each Z independently represents one selected from the group represented by the following formulas (2a) to (2c), and n is Represents an integer of 1 to 500.)

(In the formula, R3 represents an organic group having 1 to 20 carbon atoms. R represents the number of organic groups bonded to the benzene ring, and is an integer of 0 to 4. * represents Y in Formula (1). Represents the binding site.)   The resin composition according to claim 1, wherein X in the general formula (1) is an organic group having 1 to 3 carbon atoms. The resin composition according to claim 1 or 2, wherein Y in the general formula (1) is any structure or single bond selected from the group represented by the following formula.

(In the formula, * represents a binding site with Y in formula (1).)   The resin composition as described in any one of Claims 1-3 whose content in the resin composition of the said benzoxazine compound (A) is 1-25 mass parts with respect to 100 mass parts of resin solid content.   Furthermore, the resin composition as described in any one of Claims 1-4 containing a filler (D).   The resin composition of Claim 5 whose content in the resin composition of the said filler (D) is 50-1600 mass parts with respect to 100 mass parts of resin solid content.   Furthermore, any of the groups selected from epoxy resins, phenol resins, oxetane resins, compounds having polymerizable unsaturated groups, and benzoxazine compounds other than the benzoxazine compound (A) represented by the general formula (1) The resin composition as described in any one of Claims 1-6 containing 1 or more types.   The prepreg which has a resin composition as described in any one of Claims 1-7 impregnated or apply | coated to the base material and this base material.   A metal foil-clad laminate comprising the prepreg according to claim 8 and at least one laminated metal foil disposed on one or both sides of the prepreg.   The resin sheet which has the resin composition as described in any one of Claims 1-7 distribute | arranged to the surface of the support body and 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 1-7.