WO2019230942A1 - Resin composition, prepreg, metal foil laminated plate, resin sheet, and printed wiring board - Google Patents

Abstract

Provided is a resin composition whereby a cured material having excellent copper foil adhesion and low dielectric characteristics can be formed. A resin composition including a thermoplastic polymer (A) including any one or more groups from among the group consisting of a nitrile group, an epoxy group, an allyl group, a vinyl group, a carboxy group, an alkoxysilyl group, an acrylic group, a methacrylic group, a phenyl group, and a phenol-based hydroxyl group, a maleimide compound (B), and/or a cyanic acid ester compound (C), the functional group equivalent ratio represented by formula (i) thereof being 0.005-0.2. (i): Functional group equivalent ratio = (a)/((b) + (c)). (In formula (i), (a), (b), and (c) are the functional group equivalent weight (g/eq.) of the thermoplastic polymer (A), the maleimide compound (B), and the cyanic acid ester compound (C), respectively.)

Description

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

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

In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. 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 printed wiring board resins having excellent heat resistance and low dielectric properties. In recent years, resin compositions in which an epoxy resin, a bismaleimide compound, and the like are used in combination with a cyanate ester compound have been widely used for high-performance printed wiring board materials such as semiconductor plastic packages.
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. Accordingly, studies are being actively conducted to improve the reliability of the substrate by improving the adhesion between the copper foil and the resin used in the build-up layer.

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

As characteristics required for an insulating layer of a printed wiring board, it is required to have excellent adhesion to a metal foil (particularly copper foil), low dielectric loss tangent, and excellent low dielectric characteristics. In recent years, it has been desired that these characteristics be compatible at a higher level.

The present invention relates to a resin composition capable of realizing a printed wiring board excellent in adhesion and low dielectric properties of metal foil (particularly copper foil), and a prepreg, a metal foil-clad laminate, a resin sheet and printed wiring using the same. To provide a board.

As a result of intensive studies on the above problems, the present inventors have selected from the group consisting of nitrile group, epoxy group, allyl group, vinyl group, carboxy group, alkoxysilyl group, acrylic group, methacrylic group, phenyl group and phenolic hydroxyl group. The resin composition containing the thermoplastic polymer (A) containing at least one functional group and the maleimide compound (B) and / or the cyanate ester compound (C) in a predetermined ratio is a high metal foil (in particular, copper Foil) The present inventors have found that a cured product having low adhesion and dielectric loss tangent and having excellent low dielectric properties can be obtained, and the present invention has been achieved. That is, the present invention is as follows.

[1] Thermoplastic containing at least one functional group selected from the group consisting of nitrile group, epoxy group, allyl group, vinyl group, carboxy group, alkoxysilyl group, acrylic group, methacryl group, phenyl group and phenolic hydroxyl group A resin composition comprising a polymer (A) and a maleimide compound (B) and / or a cyanate ester compound (C), wherein the functional group equivalent ratio represented by the following formula (i) is 0.005 to 0.2 A resin composition.
Functional group equivalent ratio = (a) / ((b) + (c)) (i)
(In the formula (i), (a), (b) and (c) are functional group equivalents (g / g) of the thermoplastic polymer (A), maleimide compound (B) and cyanate ester compound (C), respectively. eq.) is multiplied by each used mass.)

（式（１）中、Ｒ_１は各々独立に、水素原子、炭素数１～８のアルキル基又はフェニル基を示し、ｎ_１は１以上１０以下の整数を示す。）

（式（２）中、Ｒ_２は各々独立に、水素原子又はメチル基を示し、ｎ_２は１以上の整数を示す。）

（式（３）中、Ｒ_３は各々独立に水素原子、メチル基又はエチル基を示し、Ｒ_４は各々独立に水素原子又はメチル基を示す。） [2] The maleimide compound (B) is N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, phenylmethanemaleimide, o-phenylenebismaleimide, m -Phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane 3,3'-dimethyl-5 5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 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, 4,4′-diphenylmethane biscitraconimide, , 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, the following formula [1] including at least one selected from the group consisting of a maleimide compound represented by (1), a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3). The resin composition as described.

(In Formula (1), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₁ represents an integer of 1 to 10.)

(In Formula (2), each R ₂ independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In Formula (3), each R ₃ independently represents a hydrogen atom, a methyl group or an ethyl group, and each R ₄ independently represents a hydrogen atom or a methyl group.)

[3] The cyanate ester compound (C) is a phenol novolac type cyanate ester compound, a biphenylaralkyl type cyanate ester compound, a bisphenol A type cyanate ester compound, a diallyl bisphenol A type cyanate ester compound, or a bisphenol E type cyanide. Acid ester compound, bisphenol F type cyanate ester compound, bisphenol M type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, trisphenolmethane type cyanide The resin composition according to [1] or [2], comprising at least one selected from the group consisting of an acid and an adamantane skeleton-type cyanate ester compound.

[4] The resin composition according to any one of [1] to [3], further comprising a filler (D).

[5] The resin composition according to [4], wherein the content of the filler (D) in the resin composition is 50 to 300 parts by mass with respect to 100 parts by mass of the resin solid content.

[6] A prepreg including a base material and a layer formed from the resin composition according to any one of [1] to [5].

[7] A metal foil-clad laminate including one or more prepregs according to [6] and a metal foil disposed on one side or both sides of the prepreg.

[8] A resin sheet comprising a support and a layer formed from the resin composition according to any one of [1] to [5] disposed on the surface of the support.

[9] A printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer is the resin composition according to any one of [1] to [5] A printed wiring board comprising a layer formed from

According to the present invention, a resin composition for obtaining a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board and the like excellent in adhesion and low dielectric properties of metal foil (particularly copper foil), and the resin composition are used. Prepregs, metal foil-clad laminates, resin sheets, and printed wiring boards can be provided. Moreover, a high-performance printed wiring board can be realized by using the resin composition of the present invention, and its industrial practicality is extremely high.

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.

A resin composition according to an embodiment of the present invention (hereinafter, also referred to as “this embodiment”) includes a nitrile group, an epoxy group, an allyl group, a vinyl group, a carboxy group, an alkoxysilyl group, an acrylic group, a methacrylic group, and a phenyl group. And a resin composition containing a thermoplastic polymer (A) containing at least one functional group selected from the group consisting of phenolic hydroxyl groups and a maleimide compound (B) and / or a cyanate ester compound (C), The functional group equivalent ratio represented by formula (i) is 0.005 to 0.2.

According to the resin composition according to the present embodiment, a cured product excellent in metal foil (particularly copper foil) adhesion and low dielectric property (low dielectric loss tangent) can be formed. The reason why such an effect can be obtained is not limited, but is presumed to be due to the following reason. That is, by including a thermoplastic polymer (A) in the resin composition, it is possible to impart appropriate flexibility to the resulting cured product, and as a result, improve the adhesion of metal foil (particularly copper foil). Can do. Further, the above-mentioned functional group of the thermoplastic polymer (A) is a polar functional group, and the maleic compound (B) or cyanate ester compound is obtained when the thermoplastic polymer (A) has such a functional group. Compatibility with (C) can also be improved. The resin composition has the functional group equivalent ratio represented by the formula (i) for the thermoplastic polymer (A) and maleimide compound (B) and / or cyanate ester compound (C) having the functional group. By including in a proportion of 0.005 to 0.2, the compatibility between the thermoplastic polymer (A) and the maleimide compound (B) or cyanate ester compound (C) can be made particularly excellent. As a result, the dielectric loss tangent of the obtained cured product is lowered, and it is presumed that excellent low dielectric properties were obtained.

The thermoplastic polymer (A) used in this embodiment is a thermoplastic compound, and is a nitrile group, epoxy group, allyl group, vinyl group, carboxy group, alkoxysilyl group, acrylic group, methacryl group, phenyl group. And at least one functional group selected from the group consisting of phenolic hydroxyl groups. The thermoplastic polymer (A) has thermoplasticity, and has a nitrile group, an epoxy group, an allyl group, a vinyl group, a carboxy group, an alkoxysilyl group, an acrylic group, a methacrylic group, a phenyl group at the end or side chain of the main chain. An oligomer or polymer containing at least one functional group selected from the group consisting of phenolic hydroxyl groups is preferred. By using such a compound, the adhesiveness of the hardened | cured material obtained from a resin composition to metal foil (especially copper foil) can be made excellent.

Among the functional groups possessed by the thermoplastic polymer (A) used in this embodiment, nitrile groups and vinyl groups are preferred, and those containing nitrile groups can be more suitably used.

The thermoplastic polymer (A) used in the present embodiment is preferably rubber. The rubber is an elastic body and is a high molecular compound (for example, the number average molecular weight is 1000 or more, and the number average molecular weight is 2000 or more).
Specific examples of the thermoplastic polymer (A) used in the present embodiment include, for example, acrylonitrile butadiene rubber, styrene butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, ethylene propylene rubber and the like, and among them, acrylonitrile butadiene rubber. Styrene butadiene rubber is preferred.
A commercially available thermoplastic polymer (A) may be used. For example, as the acrylonitrile butadiene rubber, JSR Co., Ltd. product, N220S (functional group equivalent 122 g / eq), etc. can be used conveniently. As the styrene butadiene rubber, L-SBR820 (functional group equivalent: 154 g / eq), L-SBR841 (functional group equivalent: 179 g / eq) manufactured by Kuraray Co., Ltd. can be preferably used. Hardened | cured material of the resin composition containing these has an effect which metal foil (especially copper foil) adhesiveness improves.
Moreover, the form which does not contain silicone type rubber is illustrated as one Embodiment of the thermoplastic polymer (A) used by this embodiment.

The functional group equivalent (g / eq) of the thermoplastic polymer (A) used in this embodiment is the number of functional groups of the compound (nitrile group, epoxy group, allyl group, vinyl group, The total number of carboxy group, alkoxysilyl group, acrylic group, methacryl group, phenyl group and phenolic hydroxyl group). When two or more kinds of thermoplastic polymers (A) are included, the functional group equivalent of each compound is multiplied by the mass content of each compound, and the sum is taken as the functional group equivalent. Hereinafter, the functional group equivalents of the maleimide compound (B) and the cyanate ester compound (C) are considered in the same manner.
The lower limit value of the functional group equivalent of the thermoplastic polymer (A) is preferably 100 g / eq or more, and more preferably 110 g / eq or more. The upper limit value of the functional group equivalent of the thermoplastic polymer (A) is preferably 200 g / eq or less, and more preferably 190 g / eq or less.
The number average molecular weight of the thermoplastic polymer (A) used in the present embodiment is, for example, 1,000 to 200,000.

The content of the thermoplastic polymer (A) in the resin composition according to the present embodiment can be appropriately set according to desired properties, and is not particularly limited, but is 100 parts by mass of resin solids in the resin composition. Of these, 1 to 50 parts by mass is preferred. When the content of the thermoplastic polymer (A) is in the range of 1 to 50 parts by mass, a resin composition having excellent metal (copper foil) adhesion can be obtained. The lower limit of the content of the thermoplastic polymer (A) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 8 parts by mass or more. The upper limit of the content of the thermoplastic polymer (A) is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, further preferably 40 parts by mass or less, and 20 parts by mass. More preferably, it is 15 parts by mass or less. The thermoplastic polymer (A) may contain only one type or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
Here, unless otherwise specified, the “resin solid content in the resin composition” refers to a component excluding the solvent and the filler (D) in the resin composition, and the resin solid content of 100 parts by mass refers to the resin. The total of the components excluding the solvent and filler (D) in the composition is 100 parts by mass.

In the resin composition according to the present embodiment, the maleimide compound (B) and the cyanate ester compound (C) may contain either one, but it is preferable from the viewpoint of heat resistance to contain both of them.

As a maleimide compound (B) used by this embodiment, there is no limitation in particular and a well-known thing can be used. By using the maleimide compound (B), the heat resistance of the cured product obtained by curing the resin composition can be improved.
Specific examples of the maleimide compound (B) include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, phenylmethanemaleimide, o-phenylenebismaleimide, m -Phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 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, 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-citraconimide) Phenyl) methane, bis (3,5-diethyl-4-citraconimidophenyl) methane, front Maleimide compound represented by the formula (1), the formula (2) maleimide compound represented by, and maleimide compounds represented by the formula (3). These maleimide compounds may be used alone or in combination of two or more. Also, a prepolymer of a maleimide compound or a prepolymer of a maleimide compound and an amine compound can be used. A commercially available product may be used as the maleimide compound (B).

The lower limit of the functional group equivalent (maleimide group equivalent) of the maleimide compound (B) is preferably 150 g / eq or more, and more preferably 160 g / eq or more. The upper limit value of the functional group equivalent of the maleimide compound (B) is preferably 240 g / eq or less, and more preferably 230 g / eq or less.

The content of the maleimide compound (B) in the resin composition according to 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, the amount is preferably 1 to 93 parts by mass. The lower limit of the content of the maleimide compound (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more. The upper limit of the content of the maleimide compound (B) is preferably 90 parts by mass or less, may be 40 parts by mass or less, and may be 35 parts by mass or less. Maleimide compound (B) may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
The number average molecular weight of the maleimide compound (B) used in the present embodiment is, for example, 200 to 10,000.

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

（式（４）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、シアン酸エステル化合物（Ｃ）は、ｔが異なる化合物の混合物であってもよい。Ｚ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。） Examples of the cyanate ester compound (C) include those represented by the formula (4).

(In formula (4), 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. Each Ra may independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a substituent. An alkoxy group having 1 to 4 carbon atoms, an aralkyl group which may have a substituent in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded, or an alkyl group having 1 to 6 carbon atoms; It is selected from any one of alkylaryl groups which may have a substituent bonded to an aryl group having 6 to 12 carbon atoms, p represents the number of cyanato groups bonded to Ar ₁ , and 1 to 3 is an integer .q represents the number of Ra to bind to Ar _1, Ar ₁ is phenylene 4-p for a group, 6-p for a naphthylene group, and 8-p for a biphenylene group, t represents an average number of repetitions and is an integer of 0 to 50, and is a cyanate ester compound (C ) May be a mixture of compounds having different t. Each Z independently represents a single bond or a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a heteroatom). A divalent organic group having 1 to 10 nitrogen atoms (—N—R—N—, etc.), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group (— OC (═O) O—), a sulfonyl group (—SO ₂ —), or a divalent sulfur atom or a divalent oxygen atom.

The alkyl group in Ra of Formula (4) may have either a chain structure (straight chain structure or branched structure) or a cyclic structure (cycloalkyl group or the like).
Moreover, the hydrogen atom in the alkyl group in Formula (4) and the aryl group in Ra 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, 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, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
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. Group, methoxyphenyl group, o-, m- or p-tolyl group.
Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like.
Specific examples of the divalent organic group in Z in the formula (4) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, and dimethylmethylene-phenylene. -Dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. 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, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in Z of formula (4) include an imino group and a polyimide group.

（式（５）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、並びに、トリフルオロメチル基及びフェノール性ヒドロキシ基の少なくとも１つにより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、シアン酸エステル化合物（Ｃ）は、ｕが異なる基を有数する化合物の混合物であってもよい。）

（式（６）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のアルコキシ基、並びに、ヒドロキシ基、トリフルオロメチル基及びシアナト基の少なくとも１つにより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、シアン酸エステル化合物（Ｃ）は、ｖが異なる基を有する化合物の混合物であってもよい。） Moreover, as Z of Formula (4), what is a structure represented by following formula (5) or following formula (6) is mentioned.

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

(In Formula (6), Ar ₃ is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 6 to 6 carbon atoms. It is selected from any one of 12 aryl groups, benzyl groups, alkoxy groups having 1 to 4 carbon atoms, and aryl groups substituted by at least one of a hydroxy group, a trifluoromethyl group, and a cyanato group. An integer of 0 to 5 is shown, but the cyanate ester compound (C) may be a mixture of compounds having different groups for 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。）
　式（５）のＡｒ_２及び式（６）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。
　式（５）のＲｂ～Ｒｇ及び式（６）のＲｉ、Ｒｊにおけるアルキル基及びアリール基は式（４）で記載したものと同様である。 Furthermore, as Z in Formula (4), the bivalent group represented by a following formula is mentioned.

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

Examples of the cyanate ester compound represented by the formula (4) include a phenol novolac cyanate ester compound, a biphenyl aralkyl cyanate ester compound, a bisphenol A type cyanate ester compound, a diallyl bisphenol A type cyanate ester compound, Bisphenol E type cyanate ester compound, bisphenol F type cyanate ester compound, bisphenol M type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, Tris Examples thereof include phenolmethane type cyanic acid and adamantane skeleton type cyanate ester compounds.

Specific examples of the cyanate ester compound represented by the formula (4) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, 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- Cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanate Nato-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-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-si Anatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanate 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 (3-allyl-4-cyanatophenyl) Propane, 2,2-bis (4-cyanato-3-methylphenyl) propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoro Propane, 2,2-bis (4-cyanato-3,5-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) iso Tan, 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-cyanatophenyl ) Octane, 3,3-bis (4-cyanatophenyl) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) ) -2,2-dimethylpentane, 4,4-bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2, 2,4-trimethylpentane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1 -Bis (4-cyanatofe ) -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 ] Biphenyl, 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, 1 , 3-bis (4-cyanatophenyl) adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 ( 3H) -one (cyanate of phenolphthalein), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (cyanate of o-cresolphthalein), 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-si Anatophenyl) 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-cyanatoani) Lino) -6- (N-methylanilino) -1,3,5-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-cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimid Gin, 1-methyl-3,3-bis (4-cyanatophenyl) indoline-2-one, 2-phenyl-3,3-bis (4-cyanatophenyl) indoline-2-one, phenol novolac resin, Cresol novolac resin (by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with formaldehyde compounds such as formalin and paraformaldehyde in an acidic solution), trisphenol novolak resin (hydroxybenzaldehyde and phenol) In the presence of an acidic catalyst), a fluorene novolak resin (a product obtained by reacting a fluorenone compound and 9,9-bis (hydroxyaryl) fluorene in the presence of an acidic catalyst), a phenol aralkyl resin, cresol Aralkyl tree By naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar 4 _- (CH 2 _Y) which the bishalogenomethyl compounds represented by ₂ and a phenolic compound is reacted with an acid catalyst or no catalyst, Ar ₄ - _(CH 2 _oR) expressed by such bis ₂ (alkoxymethyl) compound or _Ar 4 _- presence of (CH 2 _OH) bis (hydroxymethyl) as represented by _two acidic catalyst compound and a phenol compound Those reacted below, or those obtained by polycondensation of aromatic aldehyde compounds, aralkyl compounds and phenol compounds), phenol-modified xylene formaldehyde resins (existing acidic catalysts with xylene formaldehyde resins and phenol compounds by known methods) Reacted below), modified naphthalene formaldehyde Resin (a product obtained by reacting a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure (by a known method) And a phenol resin such as a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule and dehydrated in the presence of a basic catalyst) by the same method as described above. There are no particular limitations. These cyanate ester compounds can be used alone or in combination.

Among them, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, bisphenol A type cyanate ester compound, bisphenol M type cyanate ester compound, and diallyl bisphenol type cyanate ester Are preferred, and naphthol aralkyl cyanate compounds are particularly preferred.

The cured product of the resin composition using these cyanate ester compounds has excellent properties such as heat resistance and low dielectric properties (low dielectric loss tangent).

The lower limit of the functional group equivalent (cyanate group equivalent, cyanate ester group equivalent) of the cyanate ester compound (C) is preferably 120 g / eq or more, and more preferably 130 g / eq or more. The upper limit value of the functional group equivalent of the cyanate ester compound (C) is preferably 275 g / eq or less, and more preferably 265 g / eq or less.

The content of the cyanate ester compound (C) in the resin composition according to 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 masses. In the case of parts, 1 to 93 parts by mass are preferable. The lower limit of the content of the cyanate ester compound (C) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, further preferably 60 parts by mass or more, and 70 parts by mass. Or more. The upper limit of the content of the cyanate ester compound (C) is preferably 90 parts by mass or less, may be 80 parts by mass or less, and may be 70 parts by mass or less. The cyanate ester compound (C) may contain only 1 type, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
The number average molecular weight of the cyanate ester compound (C) used in the present embodiment is, for example, 100 to 2000.

The content of the thermoplastic polymer (A) and maleimide compound (B) and / or cyanate ester compound (C) used in the present embodiment in the resin composition is a functional group equivalent represented by the following formula (i): Determined based on the ratio.
Functional group equivalent ratio = (a) / ((b) + (c)) (i)
(In the formula (i), (a), (b) and (c) are functional group equivalents (g / g) of the thermoplastic polymer (A), maleimide compound (B) and cyanate ester compound (C), respectively. eq.) is multiplied by each used mass.)
The functional group in the maleimide compound (B) means a maleimide group. The functional group in the cyanate ester compound (C) means a cyanate group (cyanate ester group).

The range of the functional group equivalent ratio represented by formula (i) is 0.005 to 0.2, preferably 0.01 or more, more preferably 0.05 or more. As an upper limit, it is preferable that it is 0.17 or less, and it is preferable that it is 0.15 or less. When the functional group equivalent ratio is in the above range, the metal foil (particularly, copper foil) adhesion and low dielectric properties of the cured resin composition are particularly good.

The total content of the maleimide compound (B) and the cyanate ester compound (C) in the resin composition according to the present embodiment is 99 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. It is preferable that The lower limit of the total content of the maleimide compound (B) and the cyanate ester compound (C) is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and 85 parts by mass. More preferably, it is the above. The upper limit of the total content of the maleimide compound (B) and the cyanate ester compound (C) is preferably 97 parts by mass or less, more preferably 95 parts by mass or less, and 92 parts by mass or less. More preferably.

The resin composition according to this embodiment preferably contains a filler (D). 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, the glass wool (E glass, T glass, D glass, S glass, including glass fine powder such as Q glass.), Hollow glass, filler inorganic such as spherical glass. These fillers can be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using these fillers, characteristics such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

Although content of the filler (D) in the resin composition which concerns on this embodiment can be suitably set according to the characteristic which desires, it is not specifically limited, The resin solid content in a resin composition is 100 mass parts. In this case, the lower limit is preferably 25 parts by mass or more, more preferably 50 parts by mass or more, 75 parts by mass or more, and 100 parts by mass or more. The upper limit value is preferably 1600 parts by mass or less, more preferably 500 parts by mass or less, further preferably 300 parts by mass or less, and may be 250 parts by mass or less, and 200 parts by mass or less. It may be. By setting it as such a range, the moldability of a resin composition becomes favorable.

In using the filler (D) here, 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 Epoxy silanes such as epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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, 2009, 2152, BYK-W996, BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. , BYK-W903, BYK-W940 and the like. The wetting and dispersing agent can be used alone or in combination of two or more.

Furthermore, in the resin composition according to the present embodiment, in addition to the thermoplastic polymer (A), the maleimide compound (B), and the cyanate ester compound (C), as long as the desired properties are not impaired. An epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, or a polyphenylene ether resin may be contained.
By using these in combination, desired properties such as flame retardancy and low dielectric properties of the cured product obtained by curing the resin composition can be improved.

As the epoxy resin, as long as it is an epoxy compound or resin having two or more epoxy groups in one molecule, a known one can be used as appropriate, and the kind thereof is not particularly limited. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolak Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic ester Compounds obtained by epoxidizing double bonds such as xyresins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamines, glycidyl esters and butadiene, compounds obtained by reaction of hydroxyl-containing silicone resins with epichlorohydrin, etc. Can be mentioned. 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 compounds can be used as long as they are compounds or resins having two or more phenolic 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.

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

As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical), 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.

（式（７）中、Ｒ_５、Ｒ_６、Ｒ_７、及びＲ_８は、各々独立に炭素数６以下のアルキル基、アリール基、ハロゲン原子、又は水素原子を表す。）
で表される構成単位の重合体を含む化合物であることが好ましい。
　前記重合体は、式（８）：

（式（８）中、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１５、Ｒ_１６は、各々独立に炭素数６以下のアルキル基又はフェニル基を表す。Ｒ_１２、Ｒ_１３、Ｒ_１４は、各々独立に水素原子、炭素数６以下のアルキル基又はフェニル基を表す。）
で表される構造、及び／又は、式（９）：

（式（９）中、Ｒ_１７，Ｒ_１８、Ｒ_１９、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、各々独立に水素原子、炭素数６以下のアルキル基又はフェニル基を表す。－Ａ－は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素である）で表される構造をさらに含んでもよい。 The resin composition according to the present embodiment can suitably contain a polyphenylene ether resin. As polyphenylene ether resin, the formula (7):

(In Formula (7), R ₅ , R ₆ , R ₇ , and R ₈ each independently represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.)
It is preferable that it is a compound containing the polymer of the structural unit represented by these.
The polymer has the formula (8):

(In Formula (8), R ₉ , R ₁₀ , R ₁₁ , R ₁₅ , R ₁₆ each independently represents an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₂ , R ₁₃ , R ₁₄ are each Independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
And / or formula (9):

(In the formula (9), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- may further include a structure represented by a straight-chain, branched or cyclic divalent hydrocarbon having 20 or less carbon atoms.

The polyphenylene ether resin is partially or fully functionalized with ethylenically unsaturated groups such as vinylbenzyl groups, epoxy groups, amino groups, hydroxyl groups, mercapto groups, carboxy groups, methacryl groups, silyl groups, etc. Modified polyphenylene ether can also be used. You may use these individually by 1 type or in combination of 2 or more types.
Examples of the modified polyphenylene ether having a terminal hydroxyl group include SA90 manufactured by SABIC Innovative Plastics. Examples of the polyphenylene ether whose terminal is a methacryl group include SA9000 manufactured by SABIC Innovative Plastics.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effects of the present invention can be obtained. For example, it can be produced by the method described in Japanese Patent No. 4591665.

The modified polyphenylene ether preferably contains a modified polyphenylene ether having an ethylenically unsaturated group at the terminal. Examples of the ethylenically unsaturated group include ethenyl group, allyl group, acrylic group, methacryl group, propenyl group, butenyl group, alkenyl group such as hexenyl group and octenyl group, cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group, vinyl Examples include alkenylaryl groups such as benzyl group and vinylnaphthyl group, with vinylbenzyl group being preferred. The terminal ethylenically unsaturated group may be single or plural, and may be the same functional group or different functional groups.

（式（１０）中、Ｘはアリール基（芳香族基）を示し、－（Ｙ－Ｏ）_ｎ４－はポリフェニレンエーテル部分を示す。Ｒ_２５、Ｒ_２６、Ｒ_２７は、各々独立に水素原子、アルキル基、アルケニル基又はアルキニル基を示し、ｎ_３は１～６の整数を示し、ｎ_４は１～１００の整数を示し、ｎ_５は１～４の整数を示す。好ましくは、ｎ_３は１以上４以下の整数であるとよく、さらに好ましくは、ｎ_３は１又は２であるとよく、理想的にはｎ_３は１であるとよい。また、好ましくは、ｎ_５は１以上３以下の整数であるとよく、さらに好ましくは、ｎ_５は１又は２であるとよく、理想的にはｎ_５は２であるとよい。）で表される構造が挙げられる。 Formula (10) as a modified polyphenylene ether having an ethylenically unsaturated group at the end:

(In the formula (10), X represents an aryl group (aromatic group), and — ( _YO ) _n4 — represents a polyphenylene ether moiety. R ₂₅ , R ₂₆ and R ₂₇ are each independently a hydrogen atom, Represents an alkyl group, an alkenyl group or an alkynyl group, n ₃ represents an integer of 1 to 6, n ₄ represents an integer of 1 to 100, and n ₅ represents an integer of 1 to 4. Preferably, n ₃ represents It may be an integer of 1 or more and 4 or less, more preferably n ₃ may be 1 or 2, and ideally n ₃ may be 1. Also preferably, n ₅ is 1 or more and 3 The following integers are preferable, and more preferably, n ₅ is 1 or 2, and ideally n ₅ is 2.

As the aryl group (aromatic group) represented by X in Formula (10), n ₅ hydrogen atoms are selected from one ring structure selected from a benzene ring structure, a biphenyl structure, an indenyl ring structure, and a naphthalene ring structure. Excluded groups (for example, a phenyl group, a biphenyl group, an indenyl group, and a naphthyl group) can be mentioned, and a biphenyl group is preferable.
Here, the aryl group represented by X is a 2,2-diphenylpropane group bonded by an alkylene group such as a diphenyl ether group bonded by an oxygen atom or a benzophenone group bonded by a carbonyl group. Etc. may be included.
The aryl group may be substituted with a general substituent such as an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group), an alkenyl group, an alkynyl group, or a halogen atom. However, since the “aryl group” is substituted on the polyphenylene ether moiety via an oxygen atom, the number of general substituents depends on the number of polyphenylene ether moieties.

As the polyphenylene ether moiety (— ( _YO ) _n4 —) in the formula (10), a structural unit represented by the formula (7), (8) or (9) can be used, and in particular, in the formula (7) It is particularly preferred that the structural unit is represented.

Further, as the modified polyphenylene ether represented by the formula (10), those having a number average molecular weight of 1000 or more and 7000 or less and a minimum melt viscosity of 50000 Pa · s or less can be preferably used.

（式（１１）中、ｎ_６は各々独立して、１～１００の整数を示す。Ｘは、Ｘは、式（１０）におけるＸにおいて２価基である以外は同義である。また、連結基－（Ｙ－Ｏ）_ｎ６－は式（１０）における－（Ｙ－Ｏ）_ｎ４－と同義である。） The modified polyphenylene ether is preferably a compound represented by the following formula (11) among the formula (10).

(In formula (11), n ₆ each independently represents an integer of 1 to 100. X is synonymous with the exception that X is a divalent group in X in formula (10). The group — ( _YO ) _n6 — has the same _{meaning as} — ( _YO ) _n4 — in formula (10).

X in the formula (10) and the formula (11) is the formula (12), the formula (13), or the formula (14), and in the formula (10),-( _YO ) _n4- and the formula (11) More preferably, — ( _YO ) _n6 — is a structure in which the formula (15) or the formula (16) is arranged, or a structure in which the formula (15) and the formula (16) are arranged at random.

（式（１３）中、Ｒ_２８、Ｒ_２９、Ｒ_３０及びＲ_３１は、各々独立に水素原子又はメチル基を表す。－Ｂ－は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

(In the formula (13), R ₂₈ , R ₂₉ , R ₃₀ and R ₃₁ each independently represents a hydrogen atom or a methyl group. —B— is a linear, branched or cyclic group having 20 or less carbon atoms. (It is a divalent hydrocarbon group.)

（式（１４）中、－Ｂ－は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である）

(In the formula (14), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms)

The method for producing the modified polyphenylene ether having the structure represented by the formula (11) is not particularly limited. For example, a bifunctional phenylene ether obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by converting the terminal phenolic hydroxyl group of the oligomer to vinyl benzyl ether.
In addition, commercially available products can be used for such modified polyphenylene ether, and for example, OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Co., Ltd. can be preferably used.

Moreover, the resin composition which concerns on 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 of dazoles or anhydrides thereof, dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylaminopyridine, 2-N-ethylanilinoethanol, tri-n-butylamine, dimethylpyridine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetra Amines such as methylbutanediamine and N-methylpiperidine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, phosphorus compounds such as diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide , Peroxides such as p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, or 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 and the viscosity of the resin composition, and is not particularly limited. Usually, however, the resin solid content in the resin composition is 100 parts by mass. On the other hand, it is 0.005 to 10 parts by mass.

Furthermore, the resin composition according to the present embodiment is not limited to various properties such as other thermosetting resins, other thermoplastic resins and oligomers, and elastomers, as long as the desired properties are not impaired. A flammable compound, various additives, etc. can be used together. 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 the resin composition according to this embodiment, the total of the thermoplastic polymer (A), the maleimide compound (B), and the cyanate ester compound (C) preferably occupies 90% by mass or more of the resin solid content. It is more preferable to occupy at least 97% by mass, and even more preferably at least 97% by mass. By setting it as such a range, the effect of this invention is exhibited more effectively.

In addition, the resin composition which concerns on this embodiment can use an organic solvent as needed. In this case, the resin composition of the present invention can be used as an embodiment (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it dissolves or is compatible with at least a part, preferably all of the above-mentioned various resin components, and the kind thereof is not particularly limited. . Specifically, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolv 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 according to the present embodiment can be prepared according to a conventional method. The thermoplastic polymer (A), the maleimide compound (B) and / or the cyanate ester compound (C), and any other optional components described above. The preparation method is not particularly limited as long as the resin composition containing the components uniformly is obtained. For example, the thermoplastic polymer (A), the bismaleimide compound (B) and the cyanate ester compound (C) are blended sequentially in a solvent, and the resin composition according to this embodiment is easily prepared by sufficiently stirring. be able to.

In addition, at the time of preparation of the resin composition, known processes (stirring, mixing, kneading process, etc.) 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 agitation, mixing, and kneading treatments 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 according to this embodiment can be used as a prepreg, an insulating layer of a printed wiring board, a semiconductor package material, and the like. For example, a prepreg can be obtained by impregnating or applying the resin composition of the present invention to a substrate and drying.
Moreover, it can be set as a resin sheet by drying the solution which melt | dissolved the resin composition which concerns on this embodiment in the solvent. The resin sheet can be used as a build-up film or a dry film solder resist.
In addition, the resin composition according to the present embodiment can be used in an uncured state in which the solvent is only dried, or can be used in a semi-cured (B-stage) state as necessary.

Hereinafter, the prepreg according to the present embodiment will be described in detail. The prepreg according to the present embodiment includes a base and a layer formed from the resin composition according to the present embodiment. For example, the prepreg according to the present embodiment is obtained by impregnating or coating the base material with the resin composition according to the present 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 and base material which concern on this embodiment. Specifically, after impregnating or applying the resin composition according to the present embodiment to a base material, it is semi-cured by a method of drying at 120 to 220 ° C. for about 2 to 15 minutes, and the like, according to the present embodiment. A prepreg 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)) with respect to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass.

As the base material used when manufacturing the prepreg according to the present embodiment, known materials 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 substrate 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 suitable for dimensional stability. 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 according to the present embodiment includes one or more prepregs according to the present embodiment and a metal foil disposed on one or both sides of the prepreg according to the present embodiment. The metal foil-clad laminate according to the present embodiment is formed by laminating one or more prepregs described above, and laminating and forming metal foil on one or both sides thereof. Specifically, one or a plurality of the above-described prepregs may be stacked, and a metal foil such as copper or aluminum may be disposed on one or both sides thereof and laminated and formed. 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. The thickness of the metal foil (copper foil) is not particularly limited, but is preferably 1.5 to 70 μm, and more preferably 3 to 35 μm. 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. Further, a multilayer board can be obtained by combining the prepreg and a separately produced wiring board for inner layers (also referred to as an inner circuit board). As a method for producing a multilayer board, for example, a 35 μm metal foil (copper foil) is placed on both surfaces of one prepreg described above, laminated under the above conditions, an inner layer circuit is formed, and this circuit is blackened The inner layer circuit board is formed by carrying out the treatment, and then the inner layer circuit board and the prepreg are alternately disposed one by one, and further, a metal foil (copper foil) is disposed on the outermost layer, and the above conditions are satisfied. Preferably, a multilayer board can be produced by laminate molding under vacuum. And the metal foil tension laminated board concerning this embodiment can be used conveniently as a printed wiring board.

The printed wiring board according to the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer is formed from the resin composition according to the present embodiment. Including layers. Such a 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 is formed of the resin composition according to the embodiment described above and a cured product thereof. At least one of them is included. That is, the above-described prepreg according to the present embodiment (base material and at least one of the resin composition according to the present embodiment impregnated or coated thereon and the cured product thereof), the metal foil-clad laminate according to the present embodiment described above. The prepreg layer of the board (a layer containing at least one of the resin composition according to this embodiment and its cured product) is composed of an insulating layer containing at least one of the resin composition according to this embodiment and its cured product. Will be.

On the other hand, the resin sheet according to the present embodiment includes a support and a layer formed from the resin composition disposed on the surface of the support. The resin sheet according to the present embodiment can be obtained by applying a solution prepared by dissolving the 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 ethylenetetrafluoroethylene 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. The support is used by forming a solution obtained by dissolving the resin composition according to the present embodiment in a solvent into a sheet having a sheet-like cavity and drying it. A single layer sheet (resin sheet) can also be obtained without any problems.

In the production of the resin sheet (single layer or laminated sheet) according to the present 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. If it is, curing of the resin composition proceeds, and therefore, a temperature of 20 ° C. to 200 ° C. is preferably 1 to 90 minutes. Further, the thickness of the resin layer of the resin sheet (single layer or laminated sheet) according to this embodiment can be adjusted by the concentration of the resin composition solution and the coating thickness according to this embodiment, and is not particularly limited. In general, when the coating thickness is thick, the solvent tends to remain during drying, so 0.1 to 500 μm is preferable.

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

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

The functional group equivalent ratio of the resin composition according to the present embodiment was calculated by the following formula (i).
Functional group equivalent ratio = (a) / ((b) + (c)) (i)
(In the formula (i), (a), (b) and (c) are functional group equivalents (g / g) of the thermoplastic polymer (A), maleimide compound (B) and cyanate ester compound (C), respectively. eq.) is multiplied by each used mass.)

Example 1
In the above formula (2), R ₂ is all hydrogen atoms and n ₂ is 1 to 3 maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd. functional group equivalent 179 g / eq) 27 parts by mass, cyanic acid 2,2-bis (4-cyanatophenyl) propane (CYTESTER (registered trademark), Mitsubishi Gas Chemical Co., Ltd., functional group equivalent 139 g / eq) 63 parts by mass as an ester compound, thermoplastic polymer (liquid having vinyl group) Styrene-butadiene-elastomer L-SBR-820 (manufactured by Kuraray Co., Ltd., functional group equivalent 154 g / eq) 10 parts by mass, fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.) 150 parts by mass, zinc octylate (Nippon Chemical Industry) A varnish (resin composition) was obtained by mixing 0.10 parts by mass. In this composition, since 10 parts by mass of the thermoplastic polymer (A) is 27 parts by mass of the maleimide compound (B) and 63 parts by mass of the cyanate ester compound (C), (a) in the formula (i) ), (B) and (c) were calculated as follows.
(A): (10/100) × 154 = 15.4
(B): (27/100) × 179 = 48.3
(C): (63/100) × 139 = 87.6
Therefore, the functional group equivalent ratio calculated based on (i) was calculated as follows.
15.4 / (48.3 + 87.6) = 0.11.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 2)
In the above formula (2), R ₂ is all hydrogen atoms and n ₂ is 1 to 3, maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd. functional group equivalent 179 g / eq) 27 parts by mass, cyanic acid 2,2-bis (4-cyanatophenyl) propane (CYTESTER (registered trademark), Mitsubishi Gas Chemical Co., Ltd., functional group equivalent 139 g / eq) 63 parts by mass as an ester compound, thermoplastic polymer (liquid having vinyl group) Styrene-butadiene-elastomer-L-SBR-841 (manufactured by Kuraray Co., Ltd., functional group equivalent 179 g / eq) 10 parts by mass, fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.) 150 parts by mass, zinc octylate (Nippon Chemical Co., Ltd.) A varnish was obtained by mixing 0.10 parts by mass of Sangyo Co., Ltd. In this composition, (a) in formula (i) is 17.9, (b) is 48.3, (c) is 87.6, and the functional group equivalent ratio calculated based on (i) is 0.00. 13.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 3)
In the formula (2), 90 parts by mass of a maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd. functional group equivalent 179 g / eq) in which R ₂ is all hydrogen atoms and n ₂ is 1 to 3, thermoplasticity 10 parts by mass of polymer (N220S JSR Co., butadiene rubber having a nitrile group, functional group equivalent 122 g / eq), 150 parts by mass of fused silica (SC2050MB, manufactured by Admatechs), zinc octylate (Nippon Chemical Co., Ltd.) A varnish was obtained by mixing 0.10 parts by mass of Sangyo Co., Ltd. In this composition (i), (a) is 12.2, (b) is 161.1, (c) is 0, and the functional group equivalent ratio calculated based on (i) is 0.08. is there.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

Example 4
90 parts by mass of SNCN (functional group equivalent 256 g / eq) obtained by Synthesis Example 1, thermoplastic polymer (N220S JSR, butadiene rubber having nitrile group, functional group equivalent 122 g / eq having nitrile group) 10 parts by mass, 150 parts by mass of fused silica (SC2050MB, manufactured by Admatechs) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were mixed to obtain a varnish. In this composition (i), (a) is 12.2, (b) is 0, (c) is 230.4, and the functional group equivalent ratio calculated based on (i) is 0.05. is there.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 5)
In the above formula (2), R ₂ is all hydrogen atoms and n ₂ is 1 to 3, maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd. functional group equivalent 179 g / eq) 27 parts by mass, cyanic acid 2,2-bis (4-cyanatophenyl) propane (CYTESTER (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., functional group equivalent 139 g / eq) 63 parts by mass as an ester compound, thermoplastic polymer (N220SJSR Co., Ltd.) , Butadiene rubber having a nitrile group, functional group equivalent 122 g / eq) 10 parts by mass, fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.) 150 parts by mass, zinc octylate (produced by Nippon Chemical Industry Co., Ltd.) 0.10 The varnish was obtained by mixing parts by mass. In this composition, (a) in formula (i) is 12.2, (b) is 48.3, (c) is 87.6, and the functional group equivalent ratio calculated based on (i) is 0.00. 09.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 6)
In formula (3), a maleimide compound in which R ₃ is a methyl group and R ₄ is an ethyl group (BMI-70 manufactured by Kay Chemical Co., Ltd., functional group equivalent 221 g / eq) 29.7 parts by mass, Synthesis Example 1 SNCN (functional group equivalent 256 g / eq) 69.3 parts by mass, thermoplastic polymer (N220S JSR Co., butadiene rubber having a nitrile group, functional group equivalent 122 g / eq) 1 part by mass, melted A varnish was obtained by mixing 150 parts by mass of silica (SC2050MB, manufactured by Admatechs Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.). In this composition, (a) in formula (i) is 1.22, (b) is 65.6, (c) is 177.4, and the functional group equivalent ratio calculated based on (i) is 0.2. 01.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 7)
In the formula (3), R ₃ is a methyl group and R ₄ is an ethyl group, a maleimide compound (BMI-70 manufactured by Kay-Isei Chemical Co., Ltd., functional group equivalent 221 g / eq), 27 parts by mass, obtained by Synthesis Example 1 63 parts by mass of SNCN (functional group equivalent 256 g / eq), thermoplastic polymer (N220S JSR, butadiene rubber having a nitrile group, functional group equivalent 122 g / eq) 10 parts by mass, fused silica (SC2050MB, Varnish was obtained by mixing 150 parts by mass of Admatechs Co., Ltd. and 0.10 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd.). In this composition, (a) in formula (i) is 12.2, (b) is 59.7, (c) is 161.3, and the functional group equivalent ratio calculated based on (i) is 0. 06.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Example 8)
In the formula (3), _{R 3} is a methyl group, maleimide compounds wherein _{R 4} is an ethyl group (BMI-70 KI Kasei Co., Ltd. functional group equivalent 221 g / eq) 22.5 parts by weight Synthesis Example 1 52.5 parts by mass of SNCN (functional group equivalent 256 g / eq) obtained by the above, 25 parts by mass of thermoplastic polymer (N220S JSR, butadiene rubber having nitrile group, functional group equivalent 122 g / eq) A varnish was obtained by mixing 150 parts by mass of silica (SC2050MB, manufactured by Admatechs Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.). In this composition, (a) in formula (i) is 30.5, (b) is 49.7, (c) is 134.4, and the functional group equivalent ratio calculated based on (i) is 0. .17.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Comparative Example 1)
In the above formula (3), 30 parts by mass of a maleimide compound (BMI-70 Kay-Isei Chemical Co., Ltd. functional group equivalent 221 g / eq) in which R ₃ is a methyl group and R ₄ is an ethyl group, obtained by Synthesis Example 1 70 parts by mass of SNCN (functional group equivalent: 256 g / eq), 150 parts by mass of fused silica (SC2050MB, manufactured by Admatechs), and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) To get a varnish.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Comparative Example 2)
In the formula (2), 30 parts by mass of maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd. functional group equivalent 179 g / eq) in which R ₂ is all hydrogen atoms and n ₂ is 1 to 3, cyanic acid As an ester compound, 70 parts by mass of 2,2-bis (4-cyanatophenyl) propane (CYTESTER (registered trademark) Mitsubishi Gas Chemical Co., Ltd. functional group equivalent 139 g / eq), fused silica (SC2050MB, Admatechs Co., Ltd.) 150 parts by mass and zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.10 parts by mass were mixed to obtain a varnish.
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Comparative Example 3)
100 parts by mass of SNCN (functional group equivalent 256 g / eq) obtained by Synthesis Example 1, 150 parts by mass of fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.), zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 10 parts by mass was mixed to obtain a resin composition. This resin composition was diluted with methyl ethyl ketone, impregnated onto a 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 60% by mass.

(Comparative Example 4)
A maleimide compound (BMI-2300, functional group equivalent 179 g / eq, manufactured by Daiwa Kasei Kogyo Co., Ltd.) wherein R ₂ is all hydrogen atoms and n ₂ is 1 to 3 in the formula (2), fused silica A varnish was obtained by mixing 150 parts by mass (SC2050MB, manufactured by Admatechs Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.).
This varnish was diluted with methyl ethyl ketone, impregnated on a 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 60% by mass.

(Comparative Example 5)
In the above formula (3), R ₃ is a methyl group, and R ₄ is an ethyl group, a maleimide compound (BMI-70 manufactured by Kay Chemical Co., Ltd., functional group equivalent 221 g / eq) 18.8 parts by mass, Synthesis Example 1 SNCN (functional group equivalent 256 g / eq) 43.8 parts by mass, thermoplastic polymer (N220S JSR, butadiene rubber having a nitrile group, functional group equivalent 122 g / eq) 37.5 parts by mass Then, 150 parts by mass of fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were mixed to obtain a resin composition. In this composition, (a) in formula (i) is 45.8, (b) is 41.4, (c) is 112.0, and the functional group equivalent ratio calculated based on (i) is 0.00. 3.
This resin composition was diluted with methyl ethyl ketone, impregnated onto a 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 60% by mass.

(Comparative Example 6)
In the above formula (3), 15 parts by mass of a maleimide compound (BMI-70 Kay-Isei Chemical Co., Ltd. functional group equivalent 221 g / eq) in which R ₃ is a methyl group and R ₄ is an ethyl group, obtained by Synthesis Example 1 35 parts by mass of SNCN (functional group equivalent: 256 g / eq), thermoplastic polymer (N220S JSR, butadiene rubber having a nitrile group, functional group equivalent: 122 g / eq), 50 parts by mass, fused silica (SC2050MB, 150 parts by mass of Admatechs Co., Ltd. and 0.10 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd.) were mixed to obtain a resin composition. In this composition, (a) in formula (i) is 61.0, (b) is 33.2, (c) is 89.6, and the functional group equivalent ratio calculated based on formula (i) is 0. .5.
This resin composition was diluted with methyl ethyl ketone, impregnated onto a 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 60% by mass.

Eight prepregs obtained in Examples 1 to 8 and Comparative Examples 1 to 6 are stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) is placed up and down at a pressure of 30 kgf / Lamination was performed at cm ² and a temperature of 220 ° C. for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.8 mm. Using the obtained metal foil-clad laminate, dielectric loss tangent measurement and copper foil peel strength measurement were performed. The results are shown in Table 1.

(Measurement method and evaluation method)
1) Copper foil peel strength: For the obtained 8-layer metal foil-clad laminate, a test piece with 12 μm metal foil (30 mm × 150 mm × 0.8 mm) was used according to JIS C6481, and the number of tests was 3. The peel strength of the copper foil was measured, and the average of the lower limit values was taken as the measured value.
2) Dielectric loss tangent (Df): Using a test piece obtained by removing the copper foil of the obtained eight-layer metal foil-clad laminate, a dielectric loss tangent of 10 GHz is obtained by a cavity resonator perturbation method (Agilent Technologies Agilent 8722ES). Was measured three times, and the average value was obtained. A dielectric loss tangent value at 10 GHz of 0.004 or more was determined as NG.

As is apparent from Table 1, it was confirmed that by using the resin composition of the present invention, it is possible to realize a prepreg, a printed wiring board and the like having good copper foil adhesion and excellent low dielectric properties.

The resin composition of the present invention is used in various applications such as electrical / electronic materials, machine tool materials, and aviation materials, for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminate materials, resists, build-up laminates. It can be used widely and effectively as a plate material. In particular, it can be used particularly effectively as a printed wiring board material for high integration and high density in recent information terminal equipment and communication equipment. In addition, prepregs, resin sheets, metal foil-clad laminates and printed wiring boards obtained using the resin composition of the present invention are excellent in copper foil adhesion and low dielectric properties, so their industrial practicality. Is extremely expensive.

Claims (7)

Thermoplastic polymer containing at least one functional group selected from the group consisting of nitrile group, epoxy group, allyl group, vinyl group, carboxy group, alkoxysilyl group, acrylic group, methacryl group, phenyl group and phenolic hydroxyl group ( A resin comprising a resin composition comprising A) and a maleimide compound (B) and / or a cyanate ester compound (C), wherein the functional group equivalent ratio represented by the following formula (i) is 0.005 to 0.2 Composition.
Functional group equivalent ratio = (a) / ((b) + (c)) (i)
(In the formula (i), (a), (b) and (c) are functional group equivalents (g / g) of the thermoplastic polymer (A), maleimide compound (B) and cyanate ester compound (C), respectively. eq.) is multiplied by each used mass.) The resin composition according to claim 1, further comprising a filler (D). The resin composition according to claim 2, wherein the content of the filler (D) in the resin composition is 50 to 300 parts by mass with respect to 100 parts by mass of the resin solid content. A substrate;
A prepreg comprising a layer formed from the resin composition according to any one of claims 1 to 3. The prepreg according to claim 4, wherein one or more sheets are stacked,
A metal foil-clad laminate including a metal foil disposed on one side or both sides of the prepreg. A support;
A resin sheet comprising: a layer formed from the resin composition according to any one of claims 1 to 3 disposed on a surface of the support. A printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer,
A printed wiring board, wherein the insulating layer includes a layer formed from the resin composition according to any one of claims 1 to 3.