JPWO2019230944A1 - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

Maleimide compound (A) having no siloxane bond, unmodified cyanate ester compound (B), elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and both ends. Contains at least one selected from the group consisting of silicone (C2) having a maleimide structure, and the sum of the masses of (C1) and (C2) is 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content. A resin composition in which the silicone (C2) having a maleimide structure at both ends is a maleimide-terminal silicone represented by the following formula (4). (In the formula (4), R5 independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the proportion of R5, which is a methyl group, among all R5 is 50 mol%. As described above, n3 represents an integer of 0 to 2.)

Description

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

In recent years, the high integration and miniaturization of semiconductors used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminated board for a semiconductor package (for example, a metal foil-clad laminated board) used for a printed wiring board are becoming more and more severe. The required properties include, for example, high glass transition temperature, heat resistance, high copper foil peel strength, low dielectric constant, low dielectric loss tangent property, low thermal expansion property, low water absorption and the like. In particular, in an insulator material having a large dielectric constant and a dielectric loss tangent, an electric signal is attenuated and reliability is impaired, so that a material having a small dielectric constant and a dielectric loss tangent is required. Further, since the multilayer printed wiring board has a problem of expansion of warpage, the low thermal expansion property of the insulator material is also important.

In order to obtain a printed wiring board having these improved properties, a resin composition used as a material for the printed wiring board has been studied. For example, Patent Document 1 describes a saturated thermoplastic elastomer having a styrene unit, an epoxy resin, a cyanate ester resin, and a polybutadiene as a film showing good dielectric properties in a high frequency region while ensuring compatibility of resin components. Disclosed is a combination of at least one thermosetting resin selected from the group consisting of a resin and a maleimide compound, and a resin component containing a curing agent and a curing accelerator as constituent components in a predetermined ratio.

In Patent Document 2, vinyl compounds having a specific structure and bismaleimide resins having a specific structure are used as resin compositions having a low dielectric constant and a low dielectric loss tangent and exhibiting high adhesive strength to an LCP film and a copper foil. And a polyolefin-based elastomer as a constituent component are disclosed in combination with a predetermined ratio.

Japanese Patent No. 5724503 Japanese Unexamined Patent Publication No. 2016-117554

An example of Patent Document 1 includes a saturated thermoplastic elastomer having a styrene unit and at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate ester resin, a polybutadiene resin, and a maleimide compound. It is disclosed that a film having excellent dielectric properties in a high frequency region can be provided by producing a film by a predetermined method using the composition. However, the elastomer ratio is high and there is no description about the glass transition temperature.

On the other hand, Examples of Patent Document 2 describe examples of adhesives using a resin composition containing a vinyl compound having a specific structure, a bismaleimide resin having a specific structure, and a polyolefin-based elastomer. , Copper foil peel strength, low dielectric constant and low dielectric loss tangent property are disclosed. However, there is no description about the glass transition temperature in this document either.

Therefore, an object of the present invention is that when used as a material for a printed wiring board (for example, a metal foil-clad laminate), it has excellent low dielectric constant, low dielectric adjunctivity, high glass transition temperature, and high metal foil (copper foil). It is an object of the present invention to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that simultaneously achieve peel strength.

As a result of diligent studies on the above problems, the present inventors have found that the maleimide compound (A) having no siloxane bond, the unmodified cyanate ester compound (B), and the styrene content are 17% by mass or more. , Containing at least one selected from the group consisting of an elastomer (C1) having a styrene structure at both ends and a silicone (C2) having a maleimide structure at both ends of a specific structure, and the masses of (C1) and (C2). When the sum of the above is combined so as to be 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content, the obtained resin composition is a material for a printed wiring board (for example, a laminated board, a metal foil-clad laminate) or the like. We have found that excellent low dielectric constant, low dielectric constant contact property, high glass transition temperature, and high metal foil (copper foil) peel strength can be achieved at the same time, and have reached the present invention.

（上記式（４）中、Ｒ_５は各々独立して、炭素数１〜１２の非置換又は置換の１価の炭化水素基を示し、全てのＲ_５のうちメチル基であるＲ_５の割合が５０モル％以上であり、ｎ_３は０〜２の整数を示す。）
［２］
前記シロキサン結合を有しないマレイミド化合物（Ａ）が、下記式（１）で表されるマレイミド化合物、下記式（２）で表されるマレイミド化合物及び下記式（３）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含有する、［１］に記載の樹脂組成物。

（上記式（１）中、Ｒ_１は各々独立に水素原子又はメチル基を示し、ｎ_１は１以上の整数を示す。）

（上記式（２）中、Ｒ_２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_２は１以上１０以下の整数を示す。）

（上記式（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。）
［３］
前記変性されていないシアン酸エステル化合物（Ｂ）が、フェノールノボラック型シアン酸エステル化合物、ナフトールアラルキル型シアン酸エステル化合物、ナフチレンエーテル型シアン酸エステル化合物、ビスフェノールＡ型シアン酸エステル化合物、ビスフェノールＭ型シアン酸エステル化合物、ジアリルビスフェノールＡ型シアン酸エステル化合物からなる群より選ばれる少なくとも１種を含有する、［１］又は［２］に記載の樹脂組成物。
［４］
前記スチレン含有量が１７質量％以上であり、かつ、両末端にスチレン構造を有するエラストマー（Ｃ１）が、スチレン−ブタジエンブロック共重合体、スチレン−イソプレンブロック共重合体、スチレン−水添ブタジエンブロック共重合体、スチレン−水添イソプレンブロック共重合体、スチレン−水添（イソプレン／ブタジエン）ブロック共重合体からなる群より選ばれる少なくとも１種を含有するものである、［１］〜［３］のいずれか一つに記載の樹脂組成物。
［５］
さらに、充填材（Ｄ）を含有する、［１］〜［４］のいずれか一つに記載の樹脂組成物。
［６］
前記充填材（Ｄ）の含有量が、樹脂組成物中の樹脂固形分１００質量部に対して５０〜３００質量部である、［５］に記載の樹脂組成物。
［７］
基材と、［１］〜［６］いずれか一つに記載の樹脂組成物から形成された、プリプレグ。
［８］
１枚以上重ねた［７］に記載のプリプレグと、前記プリプレグの片面又は両面に配置した金属箔とを含む金属箔張積層板。
［９］
支持体と、前記支持体の表面に配置した［１］〜［６］のいずれか一つに記載の樹脂組成物から形成される層とを含む、樹脂シート。
［１０］
絶縁層と、前記絶縁層の表面に配置した導体層とを含むプリント配線板であって、前記絶縁層が、［１］〜［６］のいずれか一つに記載の樹脂組成物から形成された層を含む、プリント配線板。That is, the present invention is as follows.
[1]
Maleimide compound (A) having no siloxane bond, unmodified cyanate ester compound (B), elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and both ends. Contains at least one selected from the group consisting of silicone (C2) having a maleimide structure, and the sum of the masses of (C1) and (C2) is 5 to 25 mass with respect to 100 parts by mass of the resin solid content. A resin composition in which the silicone (C2) having a maleimide structure at both ends thereof contains a maleimide-terminal silicone represented by the following formula (4).

(In the above formula (4), R ₅ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the ratio of _{R 5} which is a methyl group to _{all R 5} Is 50 mol% or more, and n ₃ represents an integer of 0 to 2.)
[2]
The maleimide compound (A) having no siloxane bond is composed of a maleimide compound represented by the following formula (1), a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3). The resin composition according to [1], which contains at least one selected from the group.

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

(In the above formula (2), R ₂ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₂ represents an integer of 1 or more and 10 or less.)

(In the above formula (3), R ₃ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ independently represents a hydrogen atom or a methyl group.)
[3]
The unmodified cyanate ester compound (B) is a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, a bisphenol A type cyanate ester compound, or a bisphenol M type. The resin composition according to [1] or [2], which contains at least one selected from the group consisting of a cyanate ester compound and a diallyl bisphenol A type cyanate ester compound.
[4]
The elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a styrene-hydrogenated butadiene block. [1] to [3], which contain at least one selected from the group consisting of a polymer, a styrene-hydrogenated isoprene block copolymer, and a styrene-hydrogenated (isoprene / butadiene) block copolymer. The resin composition according to any one.
[5]
The resin composition according to any one of [1] to [4], which further contains a filler (D).
[6]
The resin composition according to [5], wherein the content of the filler (D) is 50 to 300 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[7]
A prepreg formed from a base material and the resin composition according to any one of [1] to [6].
[8]
A metal leaf-clad laminate comprising one or more stacked prepregs according to [7] and metal foils arranged on one or both sides of the prepreg.
[9]
A resin sheet containing a support and a layer formed from the resin composition according to any one of [1] to [6] arranged on the surface of the support.
[10]
A printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is formed from the resin composition according to any one of [1] to [6]. Printed wiring board, including layers.

When the resin composition of the present invention is used as a material for a printed wiring board (for example, a laminated board, a metal foil-clad laminated board) or the like, excellent low dielectric constant, low dielectric loss tangent property, high glass transition temperature, high metal foil (for example) Copper foil) A prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that simultaneously achieve peel strength can be realized, and their industrial practicality is extremely high.

Hereinafter, embodiments of the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments.

[Resin composition]
The resin composition according to the present embodiment has a maleimide compound (A) having no siloxane bond, an unmodified cyanate ester compound (B), and a styrene content of 17% by mass or more, and styrene at both ends. It contains at least one selected from the group consisting of an elastomer (C1) having a structure and a silicone (C2) having a maleimide structure at both ends, and the sum of the masses of the (C1) and (C2) is the resin solid content. The silicone (C2) which is 5 to 25 parts by mass with respect to 100 parts by mass and has a maleimide structure at both ends contains a maleimide-terminal silicone represented by the formula (4). The resin composition according to the present embodiment has excellent low dielectric constant and low dielectric loss tangent when used as a material for a printed wiring board (for example, a laminated board, a metal leaf-clad laminated board) or the like by providing the above structure. It is possible to achieve high properties, high glass transition temperature, and high metal foil (copper foil) peel strength at the same time.

[Maleimide compound (A) having no siloxane bond]
The resin composition according to this embodiment contains a maleimide compound (A) having no siloxane bond. The maleimide compound (A) having no siloxane bond according to the present embodiment is not particularly limited as long as it is a maleimide compound having one or more maleimide groups in the molecule and not having a siloxane bond. As specific examples thereof, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, 4, 4'-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene Bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-maleimide phenoxy) -phenyl) propane, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) Hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, 4,4 '-Diphenylmethanebis Citraconimide, 2,2-bis [4- (4-citraconimidephenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidephenyl) methane, bis (3-ethyl-5- Examples thereof include methyl-4-citraconimidephenyl) methane, bis (3,5-diethyl-4-citraconimidephenyl) methane, and maleimide compounds represented by the above formulas (1), (2), and (3). ..
Among these, the maleimide compound represented by the formulas (1), (2) and (3) is particularly preferable in terms of low thermal expansion and heat resistance improvement, and the maleimide compound represented by the formula (1) is more preferable. ..
The maleimide compound may be used alone or in combination of two or more.

In the above formula (1), R ₁ independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Further, in the formula (1), n ₁ represents an integer of 1 or more, and _{the upper limit of n 1} is usually 10, preferably 7, from the viewpoint of solubility in an organic solvent, and more preferably. It is 5. Siloxane bond having no maleimide compound (A), n ₁ may be a mixture of two or more different compounds.

In the above formula (2), R ₂ is an independently hydrogen atom and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group). , T-butyl group, n-pentyl group, etc.), or phenyl group. Among these, from the viewpoint of improving flame resistance and metal foil (copper foil) peel strength, it is preferable that the group is selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group, and the hydrogen atom and the methyl group are selected. On the other hand, it is more preferable, and it is more preferable that it is a hydrogen atom.

In the above formula (2), 1 ≦ n ₂ ≦ 10. From the viewpoint of further excellent solvent solubility, n ₂ is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. Further, the maleimide compound (A) having no siloxane bond may be a mixture of two or more compounds having different _{n 2.}

In the above formula (3), R ₃ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ independently represents a hydrogen atom or a methyl group. From the viewpoint of being more excellent in low dielectric constant and low dielectric loss tangent property, R ₃ is preferably a methyl group or an ethyl group.

As the maleimide compound (A) having no siloxane bond used in the present embodiment, a commercially available maleimide compound may be used. For example, as the maleimide compound represented by the formula (1), "BMI" manufactured by Daiwa Kasei Kogyo Co., Ltd. -2300 "," MIR-3000 "manufactured by Nippon Kayaku Co., Ltd. as the maleimide compound represented by the formula (2), and" BMI-70 "manufactured by Daiwa Kasei Kogyo Co., Ltd. as the maleimide compound represented by the formula (3). Can be preferably used.

The content of the maleimide compound (A) having no siloxane bond in the resin composition according to the present embodiment can be appropriately set according to the desired properties and is not particularly limited. The content of the maleimide compound (A) having no siloxane bond is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass. It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 20 parts by mass or more. The upper limit of the content of the maleimide compound (A) having no siloxane bond is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, and preferably 40 parts by mass or less. More preferably, it may be 35 parts by mass or less and 30 parts by mass or less. Within the above range, high heat resistance and low water absorption tend to be further improved.
The resin composition according to the present embodiment may contain only one type of maleimide compound (A) having no siloxane bond, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

Here, the "resin solid content in the resin composition" refers to a component of the resin composition excluding the solvent and the filler (D) unless otherwise specified, and is 100 parts by mass of the resin solid content. , The total amount of the components excluding the solvent and the filler (D) in the resin composition is 100 parts by mass.

[Unmodified cyanate ester compound (B)]
The resin composition according to this embodiment contains an unmodified cyanate ester compound (B). The unmodified cyanate ester compound (B) used in the present embodiment is a compound or resin having an aromatic moiety substituted with at least one cyanato group (cyanic acid ester group) in the molecule, and is The cyanato group does not have a group in the molecule that has reacted with a functional group other than the cyanato group and the phenolic hydroxyl group (for example, a maleimide group). That is, "unmodified" means that the cyanato group does not have a group in the molecule that has reacted with a functional group (for example, a maleimide group) other than the cyanato group and the phenolic hydroxyl group.
An example of the resin composition according to the present embodiment is a varnish, but when the resin composition according to the present embodiment is semi-cured or cured, such as a prepreg produced using the varnish, the cyanato group is used. It goes without saying that some or all of them may react with the cyanato group of the other cyanate ester compound (B) molecule or with the functional group of the other resin component.
Further, within a range in which the unmodified cyanate ester compound (B) according to the present embodiment does not deviate from the gist of the present invention, the cyanato group may be combined with the cyanato group of another cyanate ester compound (B) molecule. Alternatively, it may contain a small amount of a component that has reacted with the phenolic hydroxyl group of the raw material phenol compound.

According to the present embodiment, the resin composition comprises an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and a silicone (C2) having a maleimide structure at both ends. It is considered that the thermosetting reaction of the maleimide compound (A) having no siloxane bond and the unmodified cyanate ester compound (B) can easily proceed by containing at least one selected from the group. Be done. Therefore, it is presumed that a high glass transition temperature can be achieved even when the unmodified cyanate ester compound (B) is used.

（式（５）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。Ｒ_６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１種から選択される。ｎ_４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。ｎ_５はＡｒ_１に結合するＲ_６の数を表し、Ａｒ_１がフェニレン基の場合は４−ｎ_４、ナフチレン基の場合は６−ｎ_４、ビフェニレン基の場合は８−ｎ_４である。ｎ_６は平均繰り返し数を表し、０〜５０の整数である。変性されていないシアン酸エステル化合物（Ｂ）は、ｎ_５及び／又はｎ_６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−）、及び、２価の硫黄原子又は２価の酸素原子のいずれか１種から選択される。）Examples of the unmodified cyanate ester compound (B) according to the present embodiment include those represented by the following formula (5).

(In the formula (5), Ar ₁ 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. R ₆ may independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a substituent. A good alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 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 in which an aryl group having 6 to 12 carbon atoms is bonded. N ₄ represents the number of cyanato groups bonded to Ar _{1 and 1} to 3 of an integer .n ₅ represents the number of _{R 6} to bind to Ar _1, Ar ₁ is _{4-n 4} in the case of phenylene group, _{6-n 4} in the case of naphthylene group, in the case of biphenylene group 8-n _4. n ₆ represents the average number of iterations and is an integer from 0 to 50. The unmodified cyanate ester compound (B) is a mixture of compounds with different _{n 5} and / or n _6. Z may be a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be replaced with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms, respectively. Organic group (-N-RN-, etc.), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group (-OC (= O) O-), sulfonyl It is selected from a group (-SO _2- ) and any one of a divalent sulfur atom or a divalent oxygen atom.)

_{The alkyl group in R 6} of the formula (5) may have a linear structure, a branched structure, a cyclic structure (cycloalkyl group or the like). The hydrogen atom in the aryl group in the alkyl group and R ₆ in the formula (5) include a fluorine atom, a halogen atom such as a chlorine atom, a methoxy group, an alkoxy group such as a phenoxy group, optionally substituted by cyano group Good.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group. Examples thereof include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
Specific examples of the aryl group include phenyl group, xsilyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group and trifluorophenyl. Groups, methoxyphenyl groups, o-, m- or p-tolyl groups and the like can be mentioned.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like.
Specific examples of the divalent organic group in Z of the formula (5) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, and a dimethylmethylene-phenylene. -Includes dimethylmethylene group, fluoranyl 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 a nitrogen number of 1 to 10 in Z of the formula (5) include an imino group and a polyimide group.

（式（６）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１種から選択される。Ｒ_７、Ｒ_８、Ｒ_１１、Ｒ_１２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１種から選択される。Ｒ_９、Ｒ_１０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１種から選択される。ｎ_７は０〜５の整数を示すが、変性されていないシアン酸エステル化合物（Ｂ）は、ｎ_７が異なる式（６）で表される基を有する化合物の混合物であってもよい。）

（式（７）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１種から選択される。Ｒ_１３、Ｒ_１４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１種から選択される。ｎ_８は０〜５の整数を示すが、変性されていないシアン酸エステル化合物（Ｂ）は、ｎ_８が異なる式（７）で表される基を有する化合物の混合物であってもよい。）Further, examples of Z in the formula (5) include those having a structure represented by the following formula (6) or the following formula (7).

(In the formula (6), Ar ₂ is selected from any one of a phenylene group, a naphthylene group and a biphenylene group. R ₇ , R ₈ , R ₁₁ and R ₁₂ are independently hydrogen atoms and 1 to 1 carbon atoms, respectively. It is selected from any one of an alkyl group of 6, an aryl group having 6 to 12 carbon atoms, and an aryl group substituted with at least one of a trifluoromethyl group and a phenolic hydroxy group. R ₉ , R ₁₀ Are independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxy group. N ₇ is 0. The unmodified cyanate ester compound (B), which indicates an integer of ~ 5, may be a mixture of compounds having a group in which _{n 7 is represented by a different formula (6).)}

(In the formula (7), Ar ₃ is selected from any one of a phenylene group, a naphthylene group or a biphenylene group. R ₁₃ and R ₁₄ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and carbons, respectively. Selected from any one of an aryl group having a number of 6 to 12, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and an aryl group substituted with at least one of a hydroxy group, a trifluoromethyl group and a cyanato group. Although n ₈ represents an integer of 0 to 5, the unmodified cyanate ester compound (B) _{may be a mixture of compounds in which n 8} has a group represented by a different formula (7). .)

（式中、ｎ_９は４〜７の整数を表す。Ｒ_１５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（６）のＡｒ_２及び式（７）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（６）のＲ_７〜Ｒ_１２及び式（７）のＲ_１３、Ｒ_１４におけるアルキル基及びアリール基は式（５）で記載したものと同様である。Further, as Z in the formula (5), a divalent group represented by the following formula can be mentioned.

(In the formula, n ₉ represents an integer of 4 to 7. R ₁₅ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
_{Specific examples of Ar 2 of the} formula (6) _{and Ar 3} of the formula (7) include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, and a 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 Examples thereof include a −naphthylene group, a 1,8-naphthylene group, a 1,3-naphthylene group and a 1,4-naphthylene group. The alkyl and aryl groups in R _{7 to} R ₁₂ of the formula (6) and R ₁₃ and R ₁₄ of the formula (7) are the same as those described in the formula (5).

Examples of the cyanate ester compound represented by the formula (5) include a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a biphenyl aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, and xylene. Examples thereof include a resin type cyanate ester compound, an adamantan skeleton type cyanate ester compound, a bisphenol A type cyanate ester compound, a bisphenol M type cyanate ester compound, and a diallyl bisphenol A type cyanate ester compound.

Specific examples of the cyanate ester compound represented by the formula (5) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato-. 2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-,1-Cyanato-2,4-,1-Cyanato-2,5-,1-Cyanato -2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2- (4- (4-) Cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3 -Chlorobenzene, 1-Cyanato-2,6-dichlorobenzene, 1-Cyanato-2-methyl-3-chlorobenzene, Cyanatonitrobenzene, 1-Cyanato-4-nitro-2-ethylbenzene, 1-Cyanato-2-methoxy- 4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4- Acetylbenzene, 4-Cyanatobenzaldehyde, 4-Cyanato benzoic acid methyl ester, 4-Cyanato benzoic acid phenyl ester, 1-Cyanato-4-acetaminobenzene, 4-Cyanatobenzophenone, 1-Cyanato-2,6-di -Tart-butylbenzene, 1,2-disyanatobenzene, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,4-disyanato-2-tert-butylbenzene, 1,4-disianato-2 , 4-Dimethylbenzene, 1,4-Disianato-2,3,4-Dimethylbenzene, 1,3-Disianato-2,4,6-trimethylbenzene, 1,3-Disianato-5-Methylbenzene, 1-Cyanato Or 2-cyanatonaphthalene, 1-cyanato 4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-disyanato-1,1'-binaphthyl, 1,3 -, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-disianatosinaphthalene, 2,2'-or 4,4 '-Gisiana Tobif Enyl, 4,4'-disianato octafluorobiphenyl, 2,4'-or 4,4'-disianato diphenylmethane, 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) hexa Fluoropropane, 2,2-bis (4-cyanato-3,5-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) pentane, 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1, 1-bis (4-cyanatophenyl) -2,2-dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2- Bis (4-cyanatophenyl) hexane, 2,2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-Cyanatophenyl) -3,3-dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4) -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- Cyanatophenyl) -1-phenylethane, bis (4-cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane, 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-shi) Anatophenyl) -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-disyanatobenzophenone, 1 , 3-Bis (4-Cyanatophenyl) -2-propen-1-one, Bis (4-Cyanatophenyl) ether, Bis (4-Cyanatophenyl) sulfide, Bis (4-Cyanatophenyl) sulfone, 4-Cyanato benzoic acid-4-Cyanatophenyl ester (4-Cyanatophenyl-4-Cyanatobenzoate), bis- (4-Cyanatophenyl) carbonate, 1,3-bis (4-Cyanatophenyl) adamantan , 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantan, 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-cresolphthaline), 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) Ethan, 1,1,3-Tris (4-Cyanatophenyl) Propane, α, α, α'-Tris (4-Cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1 , 1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4,6-tris (N-methyl-4-cyanatoanilino) -1,3,5- Triazine, 2,4-bis (N-methyl-) 4-Cyanatoanilino) -6- (N-methylanilino) -1,3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4'-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) phthalimidine, 1-methyl-3, 3-bis (4-cyanatophenyl) indolin-2-one, 2-phenyl-3,3-bis (4-cyanatophenyl) indolin-2-one, phenol novolac resin and cresol novolac resin (by known methods) , Phenol, alkyl-substituted phenol or halogen-substituted phenol and formaldehyde compounds such as formalin and paraformaldehyde are reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol are reacted in the presence of an acidic catalyst). Fluorenovolac resin (a reaction of a fluorenone compound and 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl. the aralkyl resin (a known _{method, Ar 4 - (CH 2 Z} ') that 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 _- (and the CH 2 _OH) bis (hydroxymethyl as represented by ₂₎ compound and a phenol compound are reacted in the presence of an acidic catalyst , Or aromatic aldehyde compound, aralkyl compound, phenol compound and polycondensation), phenol-modified xyleneformaldehyde resin (by a known method, xyleneformaldehyde resin and phenol compound are reacted in the presence of an acidic catalyst. ), Modified naphthalene formaldehyde resin (a reaction of naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resin, polynaphthylene ether structure. Phenol resins such as phenol resins (a polyvalent hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule, dehydrated and condensed in the presence of a basic catalyst by a known method) are the same as described above. Examples thereof include those that have been acid esterified by the method described in the above, but the present invention is not particularly limited. These cyanate ester compounds may be used alone or in combination of two or more.

Among these, 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, diallyl bisphenol type cyanate ester Preferably, a naphthol aralkyl type cyanate ester compound is particularly preferable.

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 constant and low dielectric loss tangent properties).

The content of the unmodified cyanate ester compound (B) in the resin composition according to the present embodiment can be appropriately set according to the desired properties and is not particularly limited. The content of the unmodified cyanate ester compound (B) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 30 parts by mass, when the resin solid content in the resin composition is 100 parts by mass. The above is more preferable, and it may be 50 parts by mass or more. The upper limit of the content of the unmodified cyanate ester compound (B) is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, when the resin solid content in the resin composition is 100 parts by mass. preferable. Within such a range, more excellent low dielectric constant and low dielectric loss tangent property can be achieved.

[Elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends]
The resin composition according to the present embodiment contains an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. Such a styrene content (also referred to as "styrene ratio") is preferable from the viewpoint of solvent solubility and compatibility with other compounds. Here, the styrene content is the mass of the styrene unit contained in the elastomer (C1) having a styrene structure at both ends (a) g, and the mass of the entire elastomer (C1) having a styrene structure at both ends (b). ) G, it is represented by (a) / (b) × 100 (unit:%). The elastomer (C1) having a styrene structure at both ends used in the present embodiment usually has two ends, but when there are three or more, it is sufficient that the elastomer (C1) having a styrene structure at two ends thereof. It is preferable that 90% or more of the ends have a styrene structure, and it is more preferable that all the ends have a styrene structure.
Examples of the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends in the resin composition according to the present embodiment include styrene-butadiene-styrene block copolymer and styrene. -Isoprene-styrene block copolymer, styrene-hydrogenated butadiene-styrene block copolymer, styrene-hydrogenated isoprene-styrene block copolymer, styrene-hydrogenated (isoprene / butadiene) -styrene block copolymer Be done. These elastomers may be used alone or in combination of two or more. By using these elastomers, excellent low dielectric constant, excellent low dielectric loss tangent property, and high glass transition temperature can be achieved at the same time.

As the styrene structure of the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, styrene having a substituent may be used. Specifically, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used.

The upper limit of the styrene content in the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends is preferably 99% by mass or less, preferably 90% by mass or less. More preferably, it is more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, and even more preferably 45% by mass or less.

As the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends in the present embodiment, a commercially available product may be used, for example, as a styrene-butadiene-styrene block copolymer. Examples include TR2630 (manufactured by JSR Corporation) and TR2003 (manufactured by JSR Corporation). Examples of the styrene-isoprene-styrene block copolymer include SIS5250 (manufactured by JSR Corporation). Examples of the styrene-hydrogenated isoprene-styrene block copolymer include SEPTON2104 (manufactured by Kuraray Co., Ltd.).

The content of the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends in the present embodiment is such that the sum of the masses of (C1) and (C2) described later is a resin solid. It is not particularly limited as long as it is 5 to 25 parts by mass with respect to 100 parts by mass, but from the viewpoint of dielectric constant, dielectric loss tangent, and metal foil (copper foil) peel strength, 5 to 20 parts by mass is used for (C1). It is preferable, and 5 to 15 parts by mass is particularly preferable. Further, (C1) and (C2) can be appropriately mixed and used.

[Silicone (C2) having a maleimide structure at both ends]
The silicone (C2) having a maleimide structure at both ends in the present embodiment is not particularly limited as long as it is a compound having a maleimide structure at both ends of the silicone structure and represented by the formula (4). By using silicone (C2) having a maleimide structure at both ends in the present embodiment, low dielectric constant, low dielectric loss tangent property, and glass transition temperature are improved while maintaining high flame resistance.

In the formula (4), R ₅ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and is preferably an unsubstituted monovalent hydrocarbon group.

The unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, and for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, and the like. Alkyl group such as pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, alkenyl group such as vinyl group, allyl group, butenyl group, penthenyl group, hexenyl group, phenyl group, trill group, xsilyl group, naphthyl Examples thereof include an aryl group such as a group and a biphenyl group, and an aralkyl group such as a benzyl group and a phenethyl group. Among these, for industrial reasons, a methyl group, an ethyl group, a phenyl group or a benzyl group is preferable, a methyl group or a phenyl group is more preferable, and a methyl group is further preferable.

In the formula (4), of all the R _5, the ratio of R ₅ is a methyl group is at least 50 mol%, preferably in more than 65 mole%, more preferably from an industrial reasons, 70 mol% or more Is. The upper limit is not particularly limited, but it is preferably 100 mol%, that is, all methyl groups.

In formula (4), n ₃ is 0 from the viewpoint of solvent solubility and compatibility with the maleimide compound (A) having no siloxane bond and the unmodified cyanate ester compound (B). Represents an integer of ~ 2. n ₃ is preferably 0 to 1, more preferably 0. The compound represented by formula (4) is, n ₃ may be a mixture of two or more different compounds.

In the present embodiment, the silicone (C2) having a maleimide structure at both ends can be used as a powder, and may be used alone or in combination of two or more.

The method for producing silicone (C2) having a maleimide structure at both ends is not particularly limited, and for example, an acid anhydride compound and a siloxane compound are dissolved in an organic solvent capable of dissolving these raw materials. A method of mixing and reacting with each other can be mentioned. If necessary, a catalyst may be used in the reaction process. Moreover, it is preferable that the reaction is carried out at a low temperature.

The acid anhydride-based compound is not particularly limited, but is phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride. Acids, methylhexahydrophthalic anhydride and the like can be mentioned. Maleic anhydride is preferred from an industrial point of view. These acid anhydride compounds may be used alone or in combination of two or more.

The siloxane compound is not particularly limited, but 1,3-bis (3-aminopropyl) tetramethyldisiloxane, bis (3-aminobutyl) tetramethyldisiloxane, bis (3-aminopropyl) tetraphenyldisiloxane, Bis (3-aminobutyl) tetraphenyldisiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (4-amino-3-methylphenyl) tetramethyldisiloxane, bis (4-aminophenyl) tetraphenyldi Examples include siloxane. From an industrial point of view, 1,3-bis (3-aminopropyl) tetramethyldisiloxane is preferable. These siloxane compounds may be used alone or in combination of two or more.

The organic solvent is not particularly limited, but is an aproton such as dimethyl sulfone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like. Sexual polar solvents, sulphons such as tetramethylene sulphon, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, Examples thereof include ketone solvents such as cyclopentanone and cyclohexanone, and aromatic solvents such as toluene and xylene. Of these, an aprotic polar solvent is preferable from the viewpoint of reactivity. These organic solvents may be used alone or in combination of two or more.

The catalyst is not particularly limited, but is an organic metal salt such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, and a metal such as zinc chloride, aluminum chloride, and tin chloride. Chloride is mentioned. Of these, cobalt naphthenate is preferable from the viewpoint of reactivity.
These catalysts may be used alone or in combination of two or more.

The content of the silicone (C2) having a maleimide structure at both ends in the resin composition according to the present embodiment is such that the sum of the masses of (C1) and (C2) is 5 to 25 with respect to 100 parts by mass of the resin solid content. The portion by mass is not particularly limited, but 10 to 20 parts by mass is particularly preferable for (C2) from the viewpoint of dielectric constant, dielectric loss tangent, and flame resistance. Further, (C1) and (C2) can be appropriately mixed and used.

[Filler (D)]
The resin composition according to the present embodiment preferably contains a filler (D) in order to improve low dielectric constant, low dielectric loss tangent property, flame resistance and low thermal expansion property. As the filler (D) used in the present embodiment, a known filler (D) can be appropriately used, and the type thereof is not particularly limited, and a filler generally used in the art can be preferably used. .. Specifically, silicas such as natural silica, molten silica, synthetic silica, amorphous silica, aerodil, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, and silicon nitride. , Aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide heat-treated to reduce a part of crystalline water), boehmite, metal hydrates such as magnesium hydroxide, oxidation Molybdenum compounds such as molybdenum and zinc molybdenate, zinc borate, zinc nitrate, 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 G20, glass short fiber (including fine glass powders such as E glass, T glass, D glass, S glass, Q glass), hollow In addition to inorganic fillers such as glass and spherical glass, organic fillers such as styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder, etc. Can be mentioned. These fillers may 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, the properties such as thermal expansion characteristics, dimensional stability, and flame resistance of the resin composition are improved.

The content of the filler (D) in the resin composition according to the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but the resin solid content in the resin composition is 100 parts by mass. If so, 50 to 1600 parts by mass is preferable, 50 to 500 parts by mass is more preferable, and 50 to 300 parts by mass is more preferable. Alternatively, the filler (D) may be 75 to 250 parts by mass or 100 to 200 parts by mass. By setting the content of the filler in this range, the moldability of the resin composition is improved.

The resin composition may contain only one type of filler (D), or may contain two or more types of filler (D). When two or more kinds are included, the total amount is preferably in the above range.

Here, when using the filler (D), it is preferable to use at least one selected from the group consisting of a silane coupling agent and a wet dispersant in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be preferably used, and the type thereof is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxylan, γ-glycidoxypropyltrimethoxysilane, β- (3,4) -Epoxycyclohexyl) Epoxysilanes such as ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxipropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N-β- (N-vinylbenzylaminoethyl)- Examples thereof include a cationic silane type such as γ-aminopropyltrimethoxysilane hydrochloride and a phenylsilane type. The silane coupling agent may be used alone or in combination of two or more. Further, as the wet dispersant, those generally used for paints can be preferably used, and the type thereof is not particularly limited. Preferably, a copolymer-based wet dispersant 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 wet dispersant may be used alone or in combination of two or more.

The content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. The content of the dispersant (particularly the wet dispersant) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

[Other ingredients]
Further, in the resin composition according to the present embodiment, a maleimide compound other than the maleimide compound (A) having no siloxane bond and the unmodified cyanate ester compound (the unmodified cyanate ester compound) are used as long as the desired properties are not impaired. Cyanic acid ester compounds other than B), elastomers other than the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and a silicone (C2) having a maleimide structure at both ends. Contains silicones, epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, polyphenylene ether compounds, styrene oligomers (excluding those corresponding to (C1)), flame retardants, curing accelerators, organic solvents, etc. May be good. By using these in combination, desired properties such as flame resistance of a cured product obtained by curing the resin composition, high metal leaf (copper foil) peel strength, and low dielectric property can be improved.
The resin composition according to the present embodiment has a maleimide compound other than the maleimide compound (A) having no siloxane bond, a cyanate ester compound other than the unmodified cyanate ester compound (B), and the styrene content. The total amount of the elastomer other than the elastomer (C1) which is 17% by mass or more and has a styrene structure at both ends and the silicone other than the silicone (C2) which has a maleimide structure at both ends is 3 of the resin solid content. It is preferably 1% by mass or less, and more preferably 1% by mass or less. With such a configuration, the effect of the present invention is more effectively exhibited.

[Epoxy resin]
The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule. For example, 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 novolac 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 novolac-type epoxy resin, phenol-aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, alicyclic type Epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, glycidyl esters, butadiene and other double-bonded epoxy compounds, hydroxyl group-containing silicone resins and compounds obtained by the reaction of epichlorohydrin, etc. Can be mentioned. These epoxy resins may be used alone or in combination of two or more. Among these, from the viewpoint of further improving flame resistance and heat resistance, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferable.

[Phenol resin]
The phenol resin is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxy groups in one molecule, and for example, a bisphenol A type phenol resin, a bisphenol E type phenol resin, a bisphenol F type phenol resin, and the like. Bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, aralkyl novolac phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac Resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, Examples thereof include polyol-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing silicone resins. These phenol resins may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin from the viewpoint of further improving flame resistance. preferable.

[Oxetane resin]
The oxetane resin is not particularly limited, and is, for example, oxetane, alkyl oxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxatan, etc.), 3-methyl-. 3-methoxymethyl oxetane, 3,3-di (trifluoromethyl) perfluoxetane, 2-chloromethyl oxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (Toa Synthetic Co., Ltd.) Product), OXT-121 (product of Toa Synthetic Co., Ltd.) and the like. These oxetane resins may be used alone or in combination of two or more.

[Benzooxazine compound]
The benzoxazine compound is not particularly limited as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and for example, bisphenol A type benzoxazine BA-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol F. Examples thereof include type benzoxazine BF-BXZ (product of Konishi Chemical Co., Ltd.) and bisphenol S type benzoxazine BS-BXZ (product of Konishi Chemical Co., Ltd.). These benzoxazine compounds may be used alone or in combination of two or more.

（式（８）中、Ｒ_１６、Ｒ_１７、Ｒ_１８、及びＲ_１９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を用いることができる。
前記化合物は、式（９）：

（式（９）中、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２６、Ｒ_２７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_２３、Ｒ_２４、Ｒ_２５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、式（１０）：

（式（１０）中、Ｒ_２８，Ｒ_２９、Ｒ_３０、Ｒ_３１、Ｒ_３２、Ｒ_３３、Ｒ_３４、Ｒ_３５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価の炭化水素基である）
で表される構造からなる群より選ばれた少なくとも１種をさらに含んでもよい。[Polyphenylene ether compound]
As the polyphenylene ether compound, the formula (8):

(In formula (8), R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ each independently represent an alkyl group, an aryl group, a halogen atom, or a hydrogen atom having 6 or less carbon atoms.)
A compound containing a polymer of the structural unit represented by is used.
The compound has the formula (9):

(In formula (9), R ₂₀ , R ₂₁ , R ₂₂ , R ₂₆ , and R ₂₇ each independently represent an alkyl group or a phenyl group having 6 or less carbon atoms. R ₂₃ , R ₂₄ , and R ₂₅ are respectively. Independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
Structure represented by and equation (10):

(In formula (10), R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , and R ₃₅ each independently represent a hydrogen atom and an alkyl group or a phenyl group having 6 or less carbon atoms. .-A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms)
It may further contain at least one selected from the group consisting of the structures represented by.

As the polyphenylene ether compound, a part or all of the terminal is functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxy group, a methacryl group, a silyl group and the like. Modified polyphenylene ether can also be used. These may be used individually by 1 type or in combination of 2 or more type.
Examples of the modified polyphenylene ether having a hydroxyl group at the end include SA90 manufactured by SABIC Innovative Plastics Co., Ltd. Examples of the modified polyphenylene ether having a methacrylic group at the end include SA9000 manufactured by SABIC Innovative Plastics Co., Ltd.

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 an alkenyl group such as an ethenyl group, an allyl group, an acrylic group, a methacrylic group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and vinyl. Examples thereof include an alkenylaryl group such as a benzyl group and a vinylnaphthyl group, and a vinylbenzyl group is preferable. The terminal ethylenically unsaturated group may be single or plural, may be the same functional group, or may be a different functional group.

（式（１１）中、Ｘはアリール基（芳香族基）を示し、−（Ｙ−Ｏ）ｎ_１０−はポリフェニレンエーテル部分を示す。Ｒ_３６、Ｒ_３７、Ｒ_３８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_１０は１〜１００の整数を示し、ｎ_１１は１〜６の整数を示し、ｎ_１２は１〜４の整数を示す。好ましくは、ｎ_１１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_１１は１又は２であるとよく、理想的にはｎ_１１は１であるとよい。また、好ましくは、ｎ_１２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_１２は１又は２であるとよく、理想的にはｎ_１２は２であるとよい。）
で表される化合物が挙げられる。ｎ_１０、ｎ_１１及びｎ_１２の少なくとも１つが異なる２種以上の化合物の混合物であってもよい。Formula (11): as a modified polyphenylene ether having an ethylenically unsaturated group at the end:

(In formula (11), X represents an aryl group (aromatic group), − (YO) n ₁₀ − represents a polyphenylene ether moiety, and R ₃₆ , R ₃₇ , and R ₃₈ are independent hydrogen atoms. , alkyl group, alkenyl group or represents an alkynyl _{group, n 10} represents an integer of 1 to _{100, n 11} represents an integer of 1 to _{6, n 12} represents an integer of 1-4. _{preferably, n 11} Is an integer of 1 or more and 4 or less, more preferably n ₁₁ is 1 or 2, ideally n ₁₁ is 1 or more, and preferably n ₁₂ is 1 or more. It is preferably an integer of 3 or less, more preferably n ₁₂ is 1 or 2, and ideally n ₁₂ is 2.)
Examples thereof include compounds represented by. It may be a mixture of two or more compounds in which at least one of _{n 10} , n ₁₁ and n _{12 is different.}

The aryl group represented by X in the formula (11), a benzene ring structure, biphenyl structure, indenyl ring structure, and one ring structure selected from a naphthalene ring structure, except for the n ₁₂ hydrogen atoms group ( For example, a phenyl group, a biphenyl group, an indenyl group, and a naphthyl group), 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 in which the above aryl group is bonded with an oxygen atom or a benzophenone group bonded with a carbonyl group. Etc. may be included.
Further, 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 with a polyphenylene ether moiety via an oxygen atom, the limit on the number of general substituents depends on the number of polyphenylene ether moieties.

As the polyphenylene ether moiety in the formula (11), the structural unit represented by the formula (8), (9), or (10) can be used, and in particular, the structural unit represented by the formula (8) is included. Is particularly preferable.

The modified polyphenylene ether represented by the formula (11) preferably has a number average molecular weight of 1000 or more and 7000 or less. Further, in the formula (1), one having a minimum melt viscosity of 50,000 Pa · s or less can be used. In particular, in the formula (1), those having a number average molecular weight of 1000 or more and 7000 or less and a minimum melt viscosity of 50,000 Pa · s or less are preferable.
The number average molecular weight is measured using gel permeation chromatography according to a conventional method. The number average molecular weight is more preferably 1000 to 3000. By setting the number average molecular weight to 1000 or more and 7000 or less, the effect of achieving both moldability and electrical properties (low dielectric constant and low dielectric loss tangent property) is more effectively exhibited.
The minimum melt viscosity is measured using a dynamic viscoelasticity measuring device according to a conventional method. The minimum melt viscosity is more preferably 500 to 50,000 Pa · s. By setting the minimum melt viscosity to 50,000 Pa · s or less, the effect of achieving both moldability and electrical characteristics is more effectively exhibited.

（式（１２）中、Ｘは、アリール基（芳香族基）であり、−（Ｙ−Ｏ）_ｎ１３−は、それぞれ独立に、ポリフェニレンエーテル部分を示し、ｎ１３は、それぞれ独立に、１〜１００の整数を示す。）
Ｘは、式（１１）におけるＸにおいて２価基である以外は同義である。連結基−（Ｙ−Ｏ）_ｎ１３−は、式（１１）における−（Ｙ−Ｏ）_ｎ１０−と同義である。また、式（１２）で表される化合物は、Ｘ又はｎ_１３が異なる２種以上の化合物の混合物であってもよい。Among the compounds represented by the formula (11), the modified polyphenylene ether is preferably a compound represented by the following formula (12).

(In formula (12), X is an aryl group (aromatic group), − ( _YO ) n13 − independently represents a polyphenylene ether moiety, and n13 independently represents 1 to 100. Indicates an integer of.)
X is synonymous except that it is a divalent group in X in the formula (11). Linking group - _{(Y-O) n13} - is in the formula _{(11) - (Y-O} ) n10 - synonymous. The compound represented by the formula (12) may be a mixture of X or n ₁₃ is two or more different compounds.

X in the formula (11) and the formula (12) is the formula (13), the formula (14), or the formula (15), and − (YO) n ₁₀ − and the formula (12) in the formula (11). In, − (YO) n ₁₃ − is more preferably a structure in which the formula (16) or the formula (17) is arranged, or a structure in which the formula (16) and the formula (17) are randomly arranged.

（式（１４）中、Ｒ_３９、Ｒ_４０、Ｒ_４１及びＲ_４２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 formula (14), R ₃₉ , R ₄₀ , R ₄₁ and R ₄₂ each independently represent 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（１５）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 formula (15), -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 (12) is not particularly limited, and for example, the bifunctional phenylene ether obtained by oxidation-coupling a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by converting the terminal phenolic hydroxyl group of the oligomer into vinylbenzyl ether.
Further, as such a modified polyphenylene ether, a commercially available product can be used, and for example, OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Chemical Company, Inc. can be preferably used.

[Styrene oligomer]
The styrene oligomer is distinguished from the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. The styrene oligomer is obtained by polymerizing any one or more of the group consisting of styrene, styrene derivatives, and vinyltoluene, and has a number average molecular weight of 178 to 1600, an average aromatic ring number of 2 to 14, and an aromatic ring number. The compound has no branched structure and has a total amount of 2 to 14 of 50% by mass or more and a boiling point of 300 ° C. or more. Specific examples of the styrene derivative include styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene.

Examples of the styrene oligomer include styrene polymer, vinyltoluene polymer, α-methylstyrene polymer, vinyltoluene-α-methylstyrene polymer, styrene-α-styrene polymer and the like. Commercially available products may be used as the styrene polymer, for example, Picolastic A5 (manufactured by Eastman Chemical Co., Ltd.), Picolastic A-75 (manufactured by Eastman Chemical Co., Ltd.), Picotex 75 (manufactured by Eastman Chemical Co., Ltd.), FTR. -8100 (manufactured by Mitsui Chemicals, Inc.) and FTR-8120 (manufactured by Mitsui Chemicals, Inc.) can be mentioned. Examples of the vinyltoluene-α-methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical Company). As α-methylstyrene polymers, Crystallex 3070 (manufactured by Eastman Chemical Company), Crystallex 3085 (manufactured by Eastman Chemical Company), Crystallex (3100), Crystallex 5140 (manufactured by Eastman Chemical Company), FMR Examples thereof include -01100 (manufactured by Mitsui Chemicals, Inc.) and FMR-0150 (manufactured by Mitsui Chemicals, Inc.). Examples of the styrene-α-styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals, Inc.). These styrene oligomers may be used alone or in combination of two or more.

The content of the styrene oligomer is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content of the resin composition, preferably from the viewpoint of low dielectric constant, low dielectric loss tangent property and chemical resistance. It is particularly preferably 15 parts by mass.

[Flame retardants]
Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromo. Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate , Cresyldiphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris (chloroethyl) phosphate, phosphate, 1,3-phenylenebis (2,6-dixylenyl phosphate), 10- (2,5-) Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Phosphoric flame retardants, aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, antimony trioxide, etc. Examples thereof include silicone flame retardants such as flame retardants, polystyrene rubbers and silicone resins. These flame retardants may be used alone or in combination of two or more. Among these, 1,3-phenylenebis (2,6-dixylenyl phosphate) is preferable because it does not easily impair the low dielectric property. The phosphorus content in the resin composition is preferably 0.1 to 5% by mass.

[Curing accelerator]
The resin composition according to the present embodiment may contain a curing accelerator for appropriately adjusting the curing rate. Examples of the curing accelerator include those commonly used as curing accelerators such as maleimide compounds, cyanate ester compounds, and epoxy resins, and organic metal salts (for example, zinc octylate, zinc naphthenate, cobalt naphthenate, etc.). Copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, etc.), phenol compounds (eg, phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol, etc.), alcohols (eg, 1-butanol, 2-ethyl) Hexanol, etc.), imidazoles (eg, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), derivatives of these imidazoles such as carboxylic acids or adducts of acid anhydrides thereof, amines, etc. (For example, dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), phosphorus compounds (for example, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphin compounds, etc.), epoxy -Imidazole adduct compounds, peroxides (eg, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, etc.), azo compounds (eg For example, azobisisobutyronitrile, etc.). The curing accelerator may be used alone or in combination of two or more.

The content of the curing accelerator may be about 0.005 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

The resin composition according to the present embodiment may contain various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, and various additives other than the above-mentioned components. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoaming agents, dispersants, leveling. Examples include agents, brighteners, polymerization inhibitors and the like. These additives may be used alone or in combination of two or more.

[Organic solvent]
The resin composition according to this embodiment may contain an organic solvent. In this case, the resin composition according to the present embodiment is in the form (solution or varnish) in which at least a part, preferably all of the above-mentioned various resin components are dissolved or compatible with an organic solvent. The organic solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatible with at least a part, preferably all of the above-mentioned various resin components, and the polar organic solvent is, for example, ketone. Classes (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (eg, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (eg, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetate, etc.) Examples include isoamyl, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) amides (eg, dimethoxyacetamide, dimethylformamide, etc.), and examples of the non-polar organic solvent include aromatic hydrocarbons (eg, toluene, xylene). Etc.). These organic solvents may be used alone or in combination of two or more.

[Resin composition]
The resin composition according to the present embodiment can be prepared according to a conventional method, and has a maleimide compound (A) having no siloxane bond, an unmodified cyanate ester compound (B), and a styrene content of 17% by mass. At least one selected from the group consisting of an elastomer (C1) having a styrene structure at both ends and a silicone (C2) having a maleimide structure at both ends, and other above-mentioned other as necessary. The preparation method is not particularly limited as long as it is a method for obtaining a resin composition uniformly containing an arbitrary component. For example, a maleimide compound (A) having no siloxane bond, an unmodified cyanate ester compound (B), and an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. The resin composition according to the present embodiment can be easily prepared by sequentially blending at least one selected from the group consisting of silicone (C2) having a maleimide structure at both ends with a solvent and sufficiently stirring the mixture. ..

In the resin composition according to the present embodiment, the sum of the masses of the maleimide compound (A) having no siloxane bond, the unmodified cyanate ester compound (B), the elastomer (C1), and the silicone (C2) is a resin. The resin solid content contained in the composition preferably occupies 90% by mass or more, more preferably 95% by mass or more, and may occupy 98% by mass or more.

[Use]
The resin composition according to this embodiment can be suitably used as an insulating layer of a printed wiring board and a material for a semiconductor package. The resin composition according to the present embodiment can be suitably used as a material for constituting a prepreg, a metal foil-clad laminate using a prepreg, a resin sheet, and a printed wiring board.

[Prepreg]
The prepreg according to the present embodiment is formed from a base material and a resin composition according to the present embodiment. The prepreg according to the present embodiment is obtained, for example, by impregnating or coating the base material with the resin composition according to the present embodiment and then semi-curing it by a method of drying at 120 to 220 ° C. for about 2 to 15 minutes. Be done. In this case, the amount of the resin composition adhered to the substrate, that is, the amount of the resin composition (including the filler (D)) with respect to the total amount of prepreg after semi-curing is preferably in the range of 20 to 99% by mass.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. As the material of the base material, for example, glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.) Examples thereof include inorganic fibers other than glass (for example, quartz) and organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. These base materials may be used alone or in combination of two or more. Among these base materials, woven fabrics that have undergone super-spreading treatment and filling treatment are preferable from the viewpoint of dimensional stability, and the base material has a thickness of 200 μm or less and a mass of 250 g / m from the viewpoint of strength and water absorption. ^{A glass woven fabric of 2} or less is preferable, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric whose surface is treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferable. From the viewpoint of electrical characteristics, a low-dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent properties such as L-glass, NE-glass, and Q-glass is more preferable.

[Metal leaf-clad laminate]
The metal foil-clad laminate according to the present embodiment includes a prepreg according to the present embodiment in which at least one or more sheets are stacked, and a metal foil arranged on one side or both sides of the prepreg. Examples of the metal leaf-clad laminate according to the present embodiment include a method in which at least one or more prepregs according to the present embodiment are laminated and metal foils are arranged on one side or both sides thereof for laminating and molding. It can be produced by arranging a metal foil such as copper or aluminum on one side or both sides and laminating and molding. The metal foil is not particularly limited as long as it is used as a material for a printed wiring board, and examples thereof include copper foils such as rolled copper foils and electrolytic copper foils. The thickness of the metal foil (copper foil) is not particularly limited and may be about 1.5 to 70 μm. Examples of the molding method include a method usually used when molding a laminated board for a printed wiring board and a multi-layer board, and more specifically, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine and the like are used. Then, a method of laminating molding at a temperature of about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm ^{2 can be mentioned.} Further, the prepreg according to the present embodiment and the wiring board for the inner layer separately produced can be combined and laminated to form a multilayer board. As a method for manufacturing a multilayer plate, for example, a metal foil (copper foil) of about 35 μm is arranged on both sides of one prepreg according to the present embodiment, laminated by the above molding method, and then an inner layer circuit is formed. , This circuit is blackened to form an inner layer circuit board, after which the inner layer circuit board and the prepreg according to the present embodiment are alternately arranged one by one, and further, a metal foil (copper) is placed on the outermost layer. A multilayer plate can be produced by arranging the foil) and laminating and molding under the above conditions, preferably under vacuum. The metal foil-clad laminate according to the present embodiment can be suitably used as a printed wiring board.

[Printed circuit board]
The printed wiring board according to the present embodiment includes an insulating layer and a conductor layer arranged on the surface of the insulating layer, and the insulating layer includes a layer formed from the resin composition according to the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. The following is an example of a method for manufacturing a printed wiring board. First, a metal foil-clad laminate such as the copper-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is produced. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the metal foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes, and further, the outer layer circuit is formed. A printed wiring board is manufactured by forming an outer layer circuit by subjecting a metal foil for etching to 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 the resin composition according to the present embodiment described above and a cured product thereof. The configuration includes at least one of them. That is, the prepreg according to the above-described embodiment (including at least one of the base material and the resin composition according to the present embodiment impregnated or coated thereto and a cured product thereof), and the metal foil according to the above-mentioned present embodiment. The layer of the resin composition of the tension laminate (the layer containing at least one of the resin composition according to the present embodiment and the cured product thereof) contains at least one of the resin composition according to the present embodiment and the cured product thereof. It will be composed of an insulating layer.

[Resin sheet]
The resin sheet according to the present embodiment includes a support and a layer formed from the resin composition according to the present embodiment arranged on the surface of the support. The resin sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin sheet is not particularly limited, but for example, the resin sheet is obtained by applying (coating) a solution prepared by dissolving the resin composition according to the present embodiment in a solvent to a support and drying the resin sheet. The method can be mentioned.

Examples of the support used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, a release film in which a release agent is applied to the surface of these films, and a polyimide. Examples thereof include an organic film base material such as a film, a conductor foil such as a copper foil and an aluminum foil, and a plate-like material such as a glass plate, a SUS plate, and an FRP, but the present invention is not particularly limited.

As a coating method (coating method), for example, a method in which a solution obtained by dissolving the resin composition according to the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Can be mentioned. Further, after drying, the support can be peeled off or etched from the resin sheet on which the support and the resin composition are laminated to obtain a single-layer sheet (resin sheet). A support is used by supplying a solution prepared by dissolving the resin composition according to the present embodiment in a solvent into a mold having a sheet-like cavity and drying the solution to form a sheet. It is also possible to obtain a single-layer sheet (resin sheet) without this.

In the production of the single-layer sheet or the resin sheet according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, but when the temperature is low, the solvent tends to remain in the resin composition and the temperature is high. Since the resin composition is cured, it is preferably at a temperature of 20 ° C. to 200 ° C. for 1 to 90 minutes. Further, in the single-layer sheet or the resin sheet, the resin composition can be used in an uncured state in which the solvent is simply dried, or if necessary, used in a semi-cured state (B-staged). You can also. Further, the thickness of the single layer or the resin layer of the resin sheet according to the present embodiment can be adjusted by the concentration of the solution of the resin composition according to the present embodiment and the coating thickness, and is not particularly limited, but is generally limited. The thicker the coating thickness, the easier it is for the solvent to remain during drying, so 0.1 to 500 μm is preferable.

(Synthesis Example 1) Synthesis of naphthol aralkyl type cyanate ester compound (SNCN) 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) 300 g (OH group equivalent 1.28 mol) and triethylamine 194.6 g (1.92 mol) ( 1.5 mol per 1 mol of hydroxy group) was dissolved in 1800 g of dichloromethane, and this was used as solution 1.
Cyanogen chloride 125.9 g (2.05 mol) (1.6 mol with respect to 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group) ), 1205.9 g of water was poured over 30 minutes while maintaining the liquid temperature at -2 to -0.5 ° C. with stirring. After pouring 1 solution, 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 added for 10 minutes. I poured it over. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.
After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the waste water after 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 target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The weight average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN ^{showed absorption of 2250 cm -1} (cyanic acid ester group) and no absorption of hydroxy group.

(Synthesis Example 2) Synthesis of silicone (C2) having a maleimide structure at both ends represented by the formula (18) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 50.5 parts of maleic anhydride and N- Add 125 parts of methylpyrrolidone and keep the temperature below 10 ° C., and add 100 parts of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (trade name: BY16-871) manufactured by Toray Dow Corning. The solution dissolved in N-methylpyrrolidone was added dropwise. After completion of the dropping, the reaction mixture was stirred at room temperature for 6 hours. Next, 11 parts of cobalt naphthenate and 102 parts of acetic anhydride were added to this reaction mixture, and the mixture was reacted at 80 ° C. for 4 hours.

While keeping the reaction mixture at 5 ° C. or lower, 500 parts of water was added and the precipitated precipitate was filtered off. The obtained solid was further washed with water and then dried _{, and the compound of the formula (18) in which R 5} was all methyl groups and n ₃ was 0 in the formula (4), 1,1'-((1,1,1). 13 parts of 3,3-tetramethyldisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis (1H-pyrrole-2,5-dione) were obtained. The yield was 53%.

(Example 1)
As the maleimide compound (A) having no siloxane bond, in the formula (1), a maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd.) containing a mixture in which _{R 1} is an all hydrogen atom and n _{1 is 1 to 3} ), 27 parts by mass, 63 parts by mass of 2,2-bis (4-cyanatophenyl) propane (CYTESTER®, manufactured by Mitsubishi Gas Chemicals, Inc.) as the unmodified cyanate ester compound (B). , Styrene-butadiene-styrene block copolymer (TR2003, manufactured by JSR Co., Ltd., styrene ratio 40% by mass) as an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. ) 10 parts by mass and 150 parts by mass of spherical silica (SC2050-MB, manufactured by Admatex Co., Ltd., average particle size 0.5 μm) as a filler (D) were mixed, and the solid content was diluted to 65% by mass with methyl ethyl ketone. I got a crocodile.

The obtained varnish is impregnated and coated on a low-dielectric glass cloth having a thickness of 0.069 mm, and dried by heating at 165 ° C. for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Then, a prepreg having a resin composition content of 60% by mass was obtained. With one and four prepregs stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) was placed on both sides, and ^{vacuumed at a pressure of 30 kg / cm 2} and a temperature of 210 ° C for 150 minutes. Pressing was performed to obtain 12 μm copper-clad laminates (metal foil-clad laminates) having thicknesses of 0.1 mm and 0.4 mm. Using the obtained copper-clad laminate, the dielectric constant, dielectric loss tangent, glass transition temperature, copper foil peel strength, and flame resistance were evaluated. The results are shown in Table 1.

(Example 2)
In Example 1, as an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, a styrene-butadiene-styrene block copolymer (TR2003, manufactured by JSR Co., Ltd., styrene). Example 1 and Example 1 except that 10 parts by mass of a styrene-isoprene-styrene block copolymer (SIS5250, manufactured by JSR Co., Ltd., styrene ratio 20% by mass) was used instead of 10 parts by mass. Similarly, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Example 3)
In Example 1, a silicone (C2) having a maleimide structure at both ends was used as a silicone (C2) having a maleimide structure at both ends without using a styrene-butadiene-styrene block copolymer (TR2003, manufactured by JSR Co., Ltd., styrene ratio 40% by mass) from Synthesis Example 2. The obtained 1,1'-((1,1,3,3-tetramethyldisiloxane-1,3-diyl) bis (propane-3,1-diyl)) bis (1H-pyrrole-2,5-) Zeon) Copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 1 except that 10 parts by mass was used. Table 2 shows the evaluation results of the obtained copper-clad laminate.

(Example 4)
As the maleimide compound (A) having no siloxane bond, in the formula (1), the maleimide compound in which R ₁ is all hydrogen atoms and n ₁ is 1 to 3 (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 28.5 parts by mass, as an unmodified cyanate ester compound (B), 66.5 parts by mass of SNCN obtained from Synthesis Example 1, a styrene content of 17% by mass or more, and a styrene structure at both ends. Styrene-butadiene-styrene block copolymer (TR2630, manufactured by JSR Co., Ltd., styrene ratio 32% by mass) as an elastomer (C1) having 5 parts by mass, and spherical silica (D) (SC2050) as a filler (D). -MB, manufactured by Admatex Co., Ltd., average particle size 0.5 μm) was mixed with 150 parts by mass, and the solid content was diluted to 65% by mass with methyl ethyl ketone to obtain a varnish. Subsequently, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Example 5)
In Example 4, as the maleimide compound (A) having no siloxane bond, 27 parts by mass of BMI-2300 used in Example 4 was used as the unmodified cyanate ester compound (B) in Example 4. As an elastomer (C1) having SNCN of 63 parts by mass, a styrene content of 17% by mass or more, and a styrene structure at both ends, TR2630 used in Example 4 was used in an amount of 10 parts by mass. Similarly, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Example 6)
In Example 4, as the maleimide compound (A) having no siloxane bond, 24 parts by mass of BMI-2300 used in Example 4 was used as the unmodified cyanate ester compound (B) in Example 4. As an elastomer (C1) having 56 parts by mass of SNCN, a styrene content of 17% by mass or more, and a styrene structure at both ends, 20 parts by mass of TR2630 used in Example 4 was used. Similarly, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 1)
As the maleimide compound (A) having no siloxane bond, in the formula (1), the maleimide compound in which R ₁ is all hydrogen atoms and n ₁ is 1 to 3 (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 30 parts by mass, as unmodified cyanate ester compound (B), 2,2-bis (4-cyanatophenyl) propane (CYTESTER®, manufactured by Mitsubishi Gas Chemicals, Inc.) 70 parts by mass, filler As (D), 150 parts by mass of spherical silica (SC2050-MB, manufactured by Admatex Co., Ltd., average particle diameter 0.5 μm) was mixed, and thereafter, the thickness was 0.1 mm and 0.4 mm in the same manner as in Example 1. A copper-clad laminate was obtained. The evaluation results of the obtained copper-clad laminate are shown in Tables 1 and 2.

(Comparative Example 2)
In Comparative Example 1, instead of using 2,2-bis (4-cyanatophenyl) propane (manufactured by CYTESTER®, Mitsubishi Gas Chemical Company, Inc.) as the unmodified cyanate ester compound (B), Copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained in the same manner as in Comparative Example 1 except that 70 parts by mass of SNCN obtained from Synthesis Example 1 was used. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 3)
In Example 3, a silicone (C2) 1,1'-((1,1,3,3-tetramethyldisiloxane-1,3-diyl) screw having a maleimide structure at both ends obtained from Synthesis Example 2) (Propane-3,1-diyl)) Bis (1H-pyrrole-2,5-dione) 10 parts by mass is not used, and instead an acrylic polymer (weight average molecular weight: 2900, ARUFON® manufactured by Toa Synthesis Co., Ltd.) is used. ) US-6170) Copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 3 except that 10 parts by mass was used. Table 2 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 4)
In Example 3, a silicone (C2) 1,1'-((1,1,3,3-tetramethyldisiloxane-1,3-diyl) screw having a maleimide structure at both ends obtained from Synthesis Example 2) (Propane-3,1-diyl)) Bis (1H-pyrrole-2,5-dione) 10 parts by mass is not used, and instead acrylic polymer (weight average molecular weight: 10000, ARUFON® manufactured by Toa Synthesis Co., Ltd.) is used. ) UC-3000) Copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 3 except that 10 parts by mass was used. Table 2 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 5)
In Example 1, a styrene-butadiene-styrene block copolymer (TR2003, manufactured by JSR Co., Ltd., styrene) which is an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. Styrene butadiene rubber (L-SBR-820, manufactured by Kuraray Co., Ltd., weight average molecular weight 8000) with butadiene at both ends or one end was used instead of 10 parts by mass. Copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 6)
In Example 4, as the maleimide compound (A) having no siloxane bond, 21 parts by mass of BMI-2300 used in Example 4 was used as the unmodified cyanate ester compound (B) in Example 4. As an elastomer (C1) having 49 parts by mass of SNCN, a styrene content of 17% by mass or more, and a styrene structure at both ends, 30 parts by mass of TR2630 used in Example 4 was used. Similarly, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained. Table 1 shows the evaluation results of the obtained copper-clad laminate.

(Comparative Example 7)
In Example 5, a styrene-butadiene-styrene block copolymer (TR2630, manufactured by JSR Co., Ltd., styrene ratio 32 mass) which is an elastomer (C1) having a styrene content of 17% or more and a styrene structure at both ends. %) Same as in Example 5 except that 10 parts by mass of a styrene-isoprene-styrene block copolymer (SIS5229, manufactured by JSR Co., Ltd., styrene ratio 15% by mass) was used instead. A copper-clad laminate having a thickness of 0.1 mm and 0.4 mm was produced. In Comparative Example 7, phase separation was observed between the components of the resin composition, and a uniform copper-clad laminate could not be obtained, so that the values of each physical property could not be obtained.

(Comparative Example 8)
As the maleimide compound (A) having no siloxane bond, in the formula (1), the maleimide compound in which R ₁ is all hydrogen atoms and n ₁ is 1 to 3 (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 27 parts by mass, 63 parts by mass of SNCN obtained from Synthesis Example 1 as the unmodified cyanate ester compound (B), R ₅ is a methyl group in the formula (4), and the portion corresponding to _{n 3 is 7.} 10 parts by mass of silicone having a maleimide structure at both ends and 150 parts by mass of spherical silica (D) (SC2050-MB, manufactured by Admatex Co., Ltd., average particle size 0.5 μm) as a filler (D) are mixed. , The solid content was diluted to 65% by mass with methyl ethyl ketone to obtain a varnish. Subsequently, copper-clad laminates having a thickness of 0.1 mm and 0.4 mm were obtained in the same manner as in Example 1. In Comparative Example 8, phase separation was observed between the components of the resin composition, and a uniform copper-clad laminate could not be obtained, so that the values of each physical property could not be obtained.

(Measurement method and evaluation method)
(1) Permittivity (Dk) and dielectric loss tangent (Df):
Using a sample obtained by removing the copper foil of a copper-clad laminate having a thickness of 0.4 mm obtained in each example and each comparative example by etching, a perturbation method cavity resonator (Agilent Technology Co., Ltd. product, Agent 8722ES) was used. The dielectric constant and dielectric loss tangent at 10 GHz were measured.
(2) Glass transition temperature:
A dynamic viscoelastic analyzer (based on JIS C6481: 1996) using a sample obtained by removing the copper foil of a copper-clad laminate having a thickness of 0.1 mm obtained in each example and each comparative example by etching. It was measured using TA instrument copper).
(3) Copper foil peel strength:
The peel strength of the copper foil was measured according to JIS C6481: 1996 using the copper-clad laminates having a thickness of 0.4 mm obtained in each Example and each Comparative Example. Those with a result of 0.5 kN / m or more are represented by ◯, and those with a result of less than 0.5 kN / m are represented by x.
(4) Flame resistance:
Compliant with the UL94 vertical combustion test method using samples obtained by removing the copper foil of the 0.4 mm thick copper-clad laminate obtained in Example 3, Comparative Example 1, Comparative Example 3, and Comparative Example 4 by etching. And evaluated.

As described above, 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, electrically insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminated materials, and the like. It can be widely and effectively used as a resist, build-up laminated board material, etc., and in particular, it can be particularly effectively used as a printed wiring board material for high integration and high density in recent information terminal equipment and communication equipment. Is. Further, the laminated plate and the metal foil-clad laminate of the present invention can simultaneously achieve excellent low dielectric constant, low dielectric loss tangent property, high glass transition temperature, and high copper foil peel strength, and thus are industrial. Practicality is extremely high.

As is clear from Table 1, a prepreg and a printed wiring board that simultaneously achieve excellent low dielectric constant, low dielectric loss tangent property, high glass transition temperature, and high copper foil peel strength by using the resin composition of the present invention. It was confirmed that such things can be realized.

Claims (10)

A maleimide compound (A) having no siloxane bond, an unmodified cyanate ester compound (B), and an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. It contains at least one selected from the group consisting of silicone (C2) having a maleimide structure at both ends.
The sum of the masses of (C1) and (C2) is 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content.
A resin composition in which the silicone (C2) having a maleimide structure at both ends contains a maleimide-terminal silicone represented by the following formula (4).

(In the above formula (4), R ₅ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the ratio of _{R 5} which is a methyl group to _{all R 5} Is 50 mol% or more, and n ₃ represents an integer of 0 to 2.) The maleimide compound (A) having no siloxane bond is composed of a maleimide compound represented by the following formula (1), a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3). The resin composition according to claim 1, which contains at least one selected from the group.

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

(In the above formula (2), R ₂ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₂ represents an integer of 1 or more and 10 or less.)

(In the above formula (3), R ₃ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ independently represents a hydrogen atom or a methyl group.) The unmodified cyanate ester compound (B) is a phenol novolac type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, a bisphenol A type cyanate ester compound, or a bisphenol M type. The resin composition according to claim 1 or 2, which contains at least one selected from the group consisting of a cyanate ester compound and a diallyl bisphenol A type cyanate ester compound. The elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a styrene-hydrogenated butadiene block. Any of claims 1 to 3, which contains at least one selected from the group consisting of a polymer, a styrene-hydrogenated isoprene block copolymer, and a styrene-hydrogenated (isoprene / butadiene) block copolymer. The resin composition according to item 1. The resin composition according to any one of claims 1 to 4, further comprising a filler (D). The resin composition according to claim 5, wherein the content of the filler (D) is 50 to 300 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. A prepreg formed from a base material and the resin composition according to any one of claims 1 to 6. A metal leaf-clad laminate comprising at least one of the prepregs according to claim 7 and metal foils arranged on one side or both sides of the prepreg. A resin sheet comprising a support and a layer formed from the resin composition according to any one of claims 1 to 6 arranged on the surface of the support. A printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is formed from the resin composition according to any one of claims 1 to 6. Including printed wiring board.