JP2018035257A - Resin composition, prepreg, metal-clad laminate, printed wiring board, and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining an insulating layer which is excellent in workability and satisfies dielectric characteristics and solder heat resistance in a high frequency region required for an insulating layer for electronic components such as a printed wiring board.SOLUTION: A resin composition contains a cyclic olefin copolymer (A) having a glass transition temperature of 150°C or higher and lower than 250°C, and a crosslinking agent (B). A ratio ((A)/(B)) of a content of the cyclic olefin copolymer (A) to a content of the crosslinking agent (B) in the resin composition is 10 or more and 200 or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a prepreg, a metal-clad laminate, a printed wiring board, and an electronic device.

In recent years, in addition to an increase in the number of wireless communication devices and the like that use a high frequency band, a higher frequency band is inevitably used due to an increase in communication speed. Accordingly, a printed wiring board having a small dielectric loss tangent is required in order to reduce transmission loss at high frequencies to the limit.
Therefore, the required characteristics of the insulating layer used for the printed wiring board are further increased, and an insulating resin material having both heat resistance and dielectric characteristics is demanded.

  As an insulating resin material used for such a printed wiring board, the resin composition containing the cyclic olefin type polymer described in patent document 1 is mentioned, for example.

Patent Document 1 (Japanese Patent Laid-Open No. 2016-37045) discloses a metal resin laminate including a resin layer and a metal foil layer provided on one or both surfaces of the resin layer, and the resin layer includes norbornene and a norbornene-based copolymer with an α-olefin, the norbornene-based copolymer having a glass transition temperature of 250 ° C. or higher and 310 ° C. or lower and a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography. There is described a metal resin laminate having a dielectric constant of 5,000 or more and 300,000 or less, a relative dielectric constant at 5 GHz of the norbornene copolymer of 2.3 or less, and a dielectric loss tangent of 4 × 10 ⁻⁴ or less. Has been.

JP 2016-37045 A

As described in the background section above, in recent years, the required characteristics of an insulating layer used for a printed wiring board have been further increased, and an insulating resin material having both heat resistance and dielectric characteristics is required.
Here, according to the study by the present inventors, a resin composition containing a norbornene copolymer having a glass transition temperature of 250 ° C. or higher and 310 ° C. or lower as described in Patent Document 1 is resistant to solder heat. Although it was excellent, it became clear that it was inferior in workability. Such a resin composition could improve the processability to some extent by raising the processing temperature. However, if the processing temperature is raised, the resin will be decomposed and deteriorated, so that the processing temperature could not be raised sufficiently.
That is, according to the study by the present inventors, the conventional resin composition containing a cyclic olefin polymer has room for improvement in terms of improving workability, dielectric properties, and solder heat resistance in a balanced manner. It became clear that there was.

  The present invention has been made in view of the above circumstances, and has an insulating layer that has excellent workability and satisfies dielectric properties and solder heat resistance in a high frequency region required for an insulating layer for an electronic component such as a printed wiring board. The resin composition which can be obtained is provided.

  As a result of intensive studies to solve the above problems, the present inventors mix a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and lower than 250 ° C. with a crosslinking agent (B) at a specific ratio. As a result, the inventors have found that the workability and solder heat resistance can be improved in a well-balanced manner while satisfying the dielectric characteristics in the high-frequency region required for an insulating layer for electronic components such as a printed wiring board, and the present invention has been completed.

  The present invention is as follows.

（上記一般式（Ｉ）において、Ｒ^３００は水素原子又は炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。）

（上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^７５〜Ｒ^７８は、互いに結合して単環または多環を形成していてもよい。）

（上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子またはＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）

（上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。）
［３］
上記［１］または［２］に記載の樹脂組成物において、
上記環状オレフィン共重合体（Ａ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
下記一般式（Ｖ）で表される繰り返し単位、下記一般式（ＶＩ）で表される繰り返し単位および下記一般式（ＶＩＩ）で表される繰り返し単位からなる群から選ばれる少なくとも１種の非共役ジエン系オレフィン由来の繰り返し単位（ｃ）の含有量が０．０５モル％以下である樹脂組成物。

（上記一般式（Ｖ）において、Ｒ^２０１からＲ^２０６は互いに同一でも異なっていてもよく、水素原子、または炭素原子数１〜２０の炭化水素基であり、Ｐは炭素原子数１〜２０の直鎖または分岐状の炭化水素基で、二重結合及び／または三重結合を含んでいてもよい。）

（上記一般式（ＶＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^１０２とＲ^１０３は互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ^７５およびＲ^７６は、互いに結合して単環または多環を形成していてもよい。）

（上記一般式（ＶＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^１０４は水素原子または炭素原子数１〜１０のアルキル基であり、ｔは０〜１０の正の整数であり、Ｒ^７５およびＲ^７６は、互いに結合して単環または多環を形成していてもよい。）
［４］
上記［２］または［３］に記載の樹脂組成物において、
上記環状オレフィン共重合体（Ａ）中の上記α−オレフィン由来の繰り返し単位（ａ）が、上記一般式（Ｉ）においてＲ^３００が炭素原子数２以上１０以下の直鎖状の炭化水素基である繰り返し単位を含む樹脂組成物。
［５］
上記［２］乃至［４］のいずれか一つに記載の樹脂組成物において、
上記環状オレフィン共重合体（Ａ）中の上記環状オレフィン由来の繰り返し単位（ｂ）が、ビシクロ［２．２．１］−２−ヘプテンおよびテトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位である樹脂組成物。
［６］
上記［２］乃至［５］のいずれか一つに記載の樹脂組成物において、
上記環状オレフィン共重合体（Ａ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
上記環状オレフィン由来の繰り返し単位（ｂ）の含有量が１０モル％以上９０モル％以下である樹脂組成物。
［７］
上記［１］乃至［６］のいずれか一つに記載の樹脂組成物において、
炭素−炭素不飽和結合を有する架橋助剤（Ｃ）をさらに含有する樹脂組成物。
［８］
上記［１］乃至［７］のいずれか一つに記載の樹脂組成物とシート状繊維基材とを含むプリプレグ。
［９］
上記［８］に記載のプリプレグと、金属箔と、を積層してなる金属張積層体。
［１０］
上記［８］に記載のプリプレグにより形成された絶縁層と、上記絶縁層上に設けられた導体層とを備えるプリント配線基板。
［１１］
上記［１０］に記載のプリント配線基板を備えた電子機器。 [1]
A resin composition comprising a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and lower than 250 ° C., and a crosslinking agent (B),
The resin composition whose ratio ((A) / (B)) of content of the said cyclic olefin copolymer (A) with respect to content of the said crosslinking agent (B) in the said resin composition is 10-200.
[2]
In the resin composition according to the above [1],
The cyclic olefin copolymer (A) is
A repeating unit (a) derived from at least one α-olefin represented by the following general formula (I);
At least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV) The resin composition containing the repeating unit (b) derived from.

(In the general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. -20 aromatic hydrocarbon groups, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring.)

(In the general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, An aliphatic hydrocarbon group which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group; And the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. And when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .)
[3]
In the resin composition according to the above [1] or [2],
When the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%,
At least one non-conjugated selected from the group consisting of a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating unit represented by the following general formula (VII) The resin composition whose content of the repeating unit (c) derived from a diene olefin is 0.05 mol% or less.

(In the general formula (V), R ²⁰¹ to R ²⁰⁶ may be the same as or different from each other, and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is one having 1 to 20 carbon atoms. (It is a linear or branched hydrocarbon group and may contain a double bond and / or a triple bond.)

(In the general formula (VI), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. An aromatic hydrocarbon group of ˜20, R ¹⁰² and R ¹⁰³ may be the same or different from each other, are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁷⁵ and R ⁷⁶ are bonded to each other And may form a monocyclic or polycyclic ring.)

(In the general formula (VII), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ˜20 aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. And may form a monocyclic or polycyclic ring.)
[4]
In the resin composition according to the above [2] or [3],
The repeating unit (a) derived from the α-olefin in the cyclic olefin copolymer (A) is a linear hydrocarbon group having R ³⁰⁰ of 2 to 10 carbon atoms in the general formula (I). A resin composition containing a certain repeating unit.
[5]
In the resin composition according to any one of the above [2] to [4],
The cyclic olefin-derived repeating unit (b) in the cyclic olefin copolymer (A) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . The resin composition which is a repeating unit derived from at least 1 type of compound chosen from 1 ^<7 >, ¹⁰ ] -3-dodecene.
[6]
In the resin composition according to any one of the above [2] to [5],
When the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%,
The resin composition whose content of the said repeating unit (b) derived from a cyclic olefin is 10 mol% or more and 90 mol% or less.
[7]
In the resin composition according to any one of the above [1] to [6],
The resin composition which further contains the crosslinking adjuvant (C) which has a carbon-carbon unsaturated bond.
[8]
A prepreg comprising the resin composition according to any one of [1] to [7] and a sheet-like fiber base material.
[9]
A metal-clad laminate obtained by laminating the prepreg according to the above [8] and a metal foil.
[10]
A printed wiring board comprising an insulating layer formed of the prepreg according to [8] above and a conductor layer provided on the insulating layer.
[11]
Electronic equipment provided with the printed wiring board according to [10] above.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the insulating layer which is excellent in workability, and can obtain the dielectric property in the high frequency area | region requested | required of the insulating layer for electronic components, such as a printed wiring board, and solder heat resistance Can be provided.

  Hereinafter, the present invention will be described based on embodiments. In the present embodiment, “A to B” indicating a numerical range represents A or more and B or less unless otherwise specified.

[Resin composition]
First, the resin composition of embodiment which concerns on this invention is demonstrated.
The resin composition according to the present embodiment includes a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and lower than 250 ° C., and a crosslinking agent (B). And ratio ((A) / (B)) of content of the cyclic olefin copolymer (A) with respect to content of the crosslinking agent (B) in the said resin composition is 10-200, Preferably it is 15 It is 100 or less and more preferably 20 or more and 50 or less.
About the insulating layer obtained by making the glass transition temperature of a cyclic olefin copolymer (A) more than the said lower limit, including a crosslinking agent (B) in said ratio in a cyclic olefin copolymer (A). Solder heat resistance can be improved while satisfying good dielectric properties and workability. Moreover, the insulation obtained by making the glass transition temperature of a cyclic olefin copolymer (A) below the said upper limit value, including a crosslinking agent (B) in said ratio in a cyclic olefin copolymer (A). Workability can be improved while satisfying good dielectric properties and solder heat resistance of the layer.
From the above, when the glass transition temperature includes the cyclic olefin copolymer (A) having a temperature of 150 ° C. or higher and lower than 250 ° C. and the crosslinking agent (B), and (A) / (B) is within the above range. In addition to being excellent in workability, it is possible to obtain an insulating layer satisfying dielectric properties and solder heat resistance in a high frequency region required for an insulating layer for electronic parts such as a printed wiring board.

Moreover, the total content of the cyclic olefin copolymer (A) and the crosslinking agent (B) in the resin composition according to the present embodiment further improves the performance balance between the dielectric properties and solder heat resistance of the resulting insulating layer. From the viewpoint, when the entire resin composition is 100% by mass, it is preferably 20% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 98% by mass or less, and further preferably 40% by mass. It is 97 mass% or less.
Hereinafter, each component will be specifically described.

<Cyclic olefin copolymer (A)>
The cyclic olefin copolymer (A) according to this embodiment is a copolymer having a glass transition temperature of 150 ° C. or higher and lower than 250 ° C. and having a repeating unit derived from the cyclic olefin as an essential structural unit.
Although the cyclic olefin compound which comprises the cyclic olefin copolymer (A) which concerns on this embodiment is not specifically limited, For example, the cyclic olefin monomer of Paragraph 0037-0063 of international publication 2006/0118261 can be mentioned. it can.

In the cyclic olefin copolymer (A) according to this embodiment, the glass transition temperature (Tg) can be controlled by, for example, the type of monomer and the charging ratio of the monomer. Tg of the cyclic olefin copolymer (A) according to this embodiment is 150 ° C. or higher and lower than 250 ° C., preferably 170 ° C. or higher and lower than 230 ° C., more preferably 180 ° C. or higher and lower than 220 ° C. When Tg is less than the above upper limit, the processability of the cyclic olefin copolymer (A) can be further improved. Moreover, the heat resistance and mechanical characteristics of the insulating layer obtained will improve that Tg is more than the said lower limit.
Here, Tg of cyclic olefin copolymer (A) in this embodiment is the value measured in the state before bridge | crosslinking with a crosslinking agent.

  The cyclic olefin copolymer (A) according to this embodiment is represented by at least one α-olefin-derived repeating unit (a) represented by the following general formula (I) and the following general formula (II). A repeating unit derived from at least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (III) and a repeating unit represented by the following general formula (IV): The thing containing is preferable.

In addition, the cyclic olefin copolymer (A) according to the present embodiment is represented by the following general formula (I) from the viewpoint of further improving workability, solder heat resistance, dielectric properties, and impregnation into a sheet-like fiber substrate. It is more preferable to contain the repeating unit (a) derived from at least one kind of α-olefin represented and the repeating unit (b) derived from at least one kind of cyclic olefin represented by the following general formula (II). .
However, the cyclic olefin copolymer (A) according to this embodiment is represented by the following general formula (V) when the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%. A repeating unit derived from at least one non-conjugated diene olefin selected from the group consisting of a repeating unit represented by the following general formula (VI) and a repeating unit represented by the following general formula (VII) (c ) Content is, for example, 0.05 mol% or less, preferably 0.01 mol% or less, from the viewpoint of improving the glass transition temperature of the cyclic olefin copolymer (A).

上記一般式（Ｉ）において、Ｒ^３００は水素原子または炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。環状オレフィン共重合体（Ａ）のガラス転移温度を向上させ、得られる絶縁層の耐熱性をより向上させる観点から、Ｒ^３００は炭素原子数２以上１０以下の直鎖状または分岐状の炭化水素基が好ましく、炭素原子数２以上１０以下の直鎖状の炭化水素基がより好ましく、炭素原子数４以上１０以下の直鎖状の炭化水素基がさらに好ましい。

In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. From the viewpoint of improving the glass transition temperature of the cyclic olefin copolymer (A) and further improving the heat resistance of the resulting insulating layer, R ³⁰⁰ is a linear or branched hydrocarbon having 2 to 10 carbon atoms. Group is preferable, a linear hydrocarbon group having 2 to 10 carbon atoms is more preferable, and a linear hydrocarbon group having 4 to 10 carbon atoms is more preferable.

上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^７５〜Ｒ^７８は互いに結合して単環または多環を形成していてもよい。

In the general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and an integer of 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms carbon atoms 3~15, R ⁷⁵ ~R ⁷⁸ may form a monocyclic or polycyclic bonded to each other.

上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子またはＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the general formula (III), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group that is a cycloalkyl group having 3 to 15 carbon atoms, carbon An aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, a carbon atom to which R ⁹³ is bonded, or a carbon atom to which R ⁹¹ is bonded May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other. Single ring It may form an aromatic ring polycyclic.

上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。

In the general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.

上記一般式（Ｖ）において、Ｒ^２０１からＲ^２０６は互いに同一でも異なっていてもよく、水素原子、または炭素原子数１〜２０の炭化水素基であり、Ｐは炭素原子数１〜２０の直鎖または分岐状の炭化水素基で、二重結合及び／または三重結合を含んでいてもよい。

In the general formula (V), R ²⁰¹ to R ²⁰⁶ may be the same or different from each other, and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is a straight chain having 1 to 20 carbon atoms. It is a chain or branched hydrocarbon group and may contain a double bond and / or a triple bond.

上記一般式（ＶＩ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^１０２とＲ^１０３は互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ^７５およびＲ^７６は、互いに結合して単環または多環を形成していてもよい。

In the general formula (VI), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ¹⁰² and R ¹⁰³ may be the same as or different from each other, and may be a hydrogen atom or 1 to 10 carbon atoms. And R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocyclic or polycyclic ring.

上記一般式（ＶＩＩ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^１０４は水素原子または炭素原子数１〜１０のアルキル基であり、ｔは０〜１０の正の整数であり、Ｒ^７５およびＲ^７６は、互いに結合して単環または多環を形成していてもよい。

In the general formula (VII), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and t is 0 to 10 It is a positive integer, and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.

(Olefin monomer)
The olefin monomer which is one of the copolymer raw materials of the cyclic olefin copolymer (A) according to this embodiment is addition-copolymerized to form the structural unit represented by the above general formula (I). Specifically, an olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) is used.

上記一般式（Ｉａ）において、Ｒ^３００は水素原子または炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。環状オレフィン共重合体（Ａ）のガラス転移温度を向上させ、得られる絶縁層の耐熱性をより向上させる観点から、Ｒ^３００は炭素原子数２以上１０以下の直鎖状または分岐状の炭化水素基が好ましく、炭素原子数２以上１０以下の直鎖状の炭化水素基がより好ましく、炭素原子数４以上１０以下の直鎖状の炭化水素基がさらに好ましい。
具体的には、Ｒ^３００が炭素原子数２以上１０以下の直鎖状または分岐状の炭化水素基である上記一般式（Ｉａ）で表されるオレフィンモノマーとしては、１−ブテン、１−ペンテン、１−へキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−へキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−へキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン等が挙げられる。中でも、１−ヘキセン、１−オクテン、１−デセンが好ましい。

In the general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. From the viewpoint of improving the glass transition temperature of the cyclic olefin copolymer (A) and further improving the heat resistance of the resulting insulating layer, R ³⁰⁰ is a linear or branched hydrocarbon having 2 to 10 carbon atoms. Group is preferable, a linear hydrocarbon group having 2 to 10 carbon atoms is more preferable, and a linear hydrocarbon group having 4 to 10 carbon atoms is more preferable.
Specifically, examples of the olefin monomer represented by the general formula (Ia) in which R ³⁰⁰ is a linear or branched hydrocarbon group having 2 to 10 carbon atoms include 1-butene and 1-pentene. 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 -Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Of these, 1-hexene, 1-octene and 1-decene are preferable.

  The cyclic olefin copolymer (A) according to the present embodiment is composed of the repeating unit (a) derived from α-olefin when the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%. The ratio is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 85 mol% or less, and further preferably 20 mol% or more and 80 mol% or less.

(Cyclic olefin monomer (b))
The cyclic olefin monomer (b), which is one of the copolymer raw materials of the cyclic olefin copolymer (A) according to the present embodiment, is addition-copolymerized to perform the above general formula (II), the above general formula (III), or the above general formula The repeating unit (b) derived from the cyclic olefin represented by the formula (IV) is formed. Specifically, the cyclic olefin represented by the general formulas (IIa), (IIIa), and (IVa) corresponding to the general formula (II), the general formula (III), and the general formula (IV), respectively. Monomer (b) is used.

上記一般式（ＩＩａ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基、または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^７５〜Ｒ^７８は、互いに結合して単環または多環を形成していてもよい。

In the general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and an integer of 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. .

上記一般式（ＩＩＩａ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子またはＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the above general formula (IIIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group that is a cycloalkyl group having 3 to 15 carbon atoms, carbon An aromatic hydrocarbon group or an alkoxy group having 6 to 20 atoms, a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, a carbon atom to which R ⁹³ is bonded, or a carbon atom to which R ⁹¹ is bonded May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other. Single ring Others may form an aromatic ring polycyclic.

上記一般式（ＩＶａ）において、Ｒ^１００、Ｒ^１０１は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。

In the general formula (IVa), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.

  By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component, Since the solubility of the polymer (A) in the solvent is further improved, the moldability is improved and the yield of the product is improved.

  As specific examples of the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006/0118261 can be used.

  Specifically, bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclo Pentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5 -Heneecocene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacocene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4 Methano -1,4,4a, 9a- tetrahydrofluorene derivatives, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene derivatives, cycloalkylene derivative having 3 to 20 carbon atoms.

  Among the cyclic olefin monomers (b) represented by the general formula (IIa), (IIIa) or (IVa), the cyclic olefin represented by the general formula (IIa) is preferable.

Examples of the cyclic olefin monomer (b) represented by the general formula (IIa) include bicyclo [2.2.1] -2-heptene (also referred to as norbornene), tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (also referred to as tetracyclododecene) is preferably used, and tetracyclo [4.4.0.1 ^2,5 . It is more preferable to use 1 ^7,10 ] -3-dodecene. Since these cyclic olefins have a rigid ring structure, it is easy to maintain the elastic modulus of the copolymer and the insulating layer, and since they do not contain a heterogeneous double bond structure, there is an advantage that the crosslinking can be easily controlled.

  The cyclic olefin copolymer (A) according to this embodiment is a repeating unit derived from the cyclic olefin monomer (b) (100 mol%) when the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%. The ratio of b) is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 85 mol% or less, and further preferably 20 mol% or more and 80 mol% or less.

The intrinsic viscosity [η] measured in decalin at 135 ° C. of the cyclic olefin copolymer (A) according to this embodiment is usually 0.01-1 dl / g, preferably 0.05-0. 7 dl / g, more preferably 0.1 to 0.5 dl / g. When the intrinsic viscosity [η] is not more than the above upper limit value, the moldability is improved. Further, when the intrinsic viscosity [η] is not less than the above lower limit value, the heat resistance and mechanical properties of the obtained insulating layer are improved.
The intrinsic viscosity [η] of the cyclic olefin copolymer (A) can be controlled by polymerization conditions such as a polymerization catalyst, a cocatalyst, an amount of H ₂ added, and a polymerization temperature.

  The cyclic olefin copolymer (A) according to the present embodiment is, for example, a method for producing a cyclic olefin (co) polymer described in paragraphs 0075 to 0219 of International Publication No. 2012/046443 or International Publication No. 2006/118261. It can manufacture according to the manufacturing method of the cyclic olefin (co) polymer of paragraphs 0095-0234. Details are omitted here.

<Crosslinking agent (B)>
The resin composition according to the present embodiment includes a crosslinking agent (B). Thereby, the solder heat resistance of the resin composition can be improved.
As a crosslinking agent (B), a radical polymerization initiator etc. are mentioned, for example. For curing with a radical polymerization initiator, a curing method using a normal radical polymerization initiator applied to polyolefin can be applied as it is. That is, a radical polymerization initiator such as dicumyl peroxide is blended in the resin composition and heated and cured.

  As said radical polymerization initiator, a well-known thermal radical polymerization initiator, radical photopolymerization initiator, and these can be used together. Among these radical polymerization initiators, when a thermal radical polymerization initiator is used, the 10-hour half-life temperature is usually 80 ° C. or higher, preferably 120 ° C. or higher, from the viewpoint of storage stability. Examples of such initiators include dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis (t-butylperoxy) 2,5-dimethylhexane, 2,5-bis (t-butylperoxide). 1) Dialkyl peroxides such as oxy) 2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, bis (α-t-butylperoxyisopropyl) benzene; , 1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, n -Butyl-4,4-bis (t-butylperoxy) valerate, ethyl-3,3-bis (t-butylperoxy) butyrate, 3,3 Peroxyketals such as 6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; bis (t-butylperoxy) isophthalate, t-butylperoxybenzoate, t-butyl Peroxyesters such as peroxyacetate; t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane Etc.

Examples of the photo radical polymerization initiator include benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methyl benzoyl formate, isopropyl Examples include thioxanthone and a mixture of two or more thereof.
Moreover, a sensitizer can also be used with these radical photopolymerization initiators. Examples of the sensitizer include anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p, p′-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranil, nitrobenzene, p-dinitrobenzene, 2- Nitro compounds such as nitrofluorene, aromatic hydrocarbons such as anthracene and chrysene, sulfur compounds such as diphenyl disulfide, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, etc. A nitrogen compound etc. can be mentioned.

  When the radical polymerization initiator cures the resin composition according to this embodiment, the curing temperature is, for example, 100 to 350 ° C., preferably 120 to 330 ° C., more preferably 150 to 300 ° C. Curing may be performed by changing in stages. When it is at least the lower limit, curing can be sufficiently advanced. Moreover, when it is below the above upper limit value, coloring of the obtained insulating layer can be suppressed or the process can be simplified.

<Crosslinking aid (C)>
The resin composition according to the present embodiment further includes a crosslinking aid (C) having a carbon-carbon unsaturated bond from the viewpoint of promoting the crosslinking reaction and further improving the solder heat resistance of the obtained insulating layer. Is preferred.
Although there is no restriction | limiting in particular as a crosslinking adjuvant (C), For example, the polyfunctional compound which has two or more isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, and o-diisopropenylbenzene Ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Multifunctionalization having two or more methacrylic groups such as 2,2′-bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate Compound; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; allyl such as hexamethylene diallyl nadiimide, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate, triallyl trimelliate Compounds; Maleimide compounds such as N, N′-m-phenylenebismaleimide and N, N ′-(4,4′-methylenediphenylene) dimaleimide; Cyclic non-conjugated such as vinylnorbornene, ethylidenenorbornene and dicyclopentadiene Dienes; such as polybutadiene. These crosslinking aids (C) may be used alone or in combination.
Among these, isocyanurates such as triallyl isocyanurate, triallyl cyanurate and triallyl trimelliate; divinylbenzene; polybutadiene are more preferable.
The polybutadiene according to the present embodiment is not particularly limited, and examples thereof include 1,4-polybutadiene, 1,2-polybutadiene, terminal acrylate-modified polybutadiene, terminal urethane methacrylate-modified polybutadiene, and the like.
Moreover, as a crosslinking adjuvant (C), the repeating unit (a) derived from the at least 1 sort (s) of alpha olefin represented by the said general formula (I), the repeating unit represented by the said general formula (II), A repeating unit (b) derived from at least one cyclic olefin selected from the group consisting of the repeating unit represented by the general formula (III) and the repeating unit represented by the general formula (IV); Derived from at least one non-conjugated diene-based olefin selected from the group consisting of a repeating unit represented by V), a repeating unit represented by the above general formula (VI), and a repeating unit represented by the above general formula (VII) A cyclic olefin copolymer containing the repeating unit (c) may be used.

  The crosslinking aid (C) can be used alone or in combination of two or more. Content of the crosslinking adjuvant (C) in the resin composition which concerns on this embodiment is 0.1-100 mass parts with respect to 100 mass parts of cyclic olefin copolymers (A), Preferably it is 0.5. -50 mass parts, More preferably, it is 1-30 mass parts.

<Other ingredients>
The resin composition according to the present embodiment includes a flame retardant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, and a natural oil as necessary. , Synthetic oils, waxes, organic fillers, inorganic fillers, thermoplastic resins other than the cyclic olefin copolymer (A) and thermosetting resins can be blended to such an extent that the object of the present invention is not impaired. The blending ratio is an appropriate amount. Specific examples of the stabilizer to be blended as an optional component include tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t. Phenol-type antioxidants such as -butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate; stearin Fatty acid metal salts such as zinc acid, calcium stearate, calcium 12-hydroxystearate; polyhydric alcohol fatty acid esters such as glycerol monostearate, glycerol monolaurate, glycerol distearate, pentaerythritol tristearate, etc. . These may be blended alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate and Examples include combinations with glycerin monostearate.

Although it does not specifically limit as a flame retardant, For example, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, chlorinated polystyrene, chlorinated polyethylene, highly chlorinated polypropylene, chlorosulfonated polyethylene , Hexabromobenzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4- Hydroxy-3,5-dibromophenylpropane), halogenated flame retardants such as pentabromotoluene; metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide; Flame retardants; nitrogen-containing flame retardant; halogen-free flame retardants such as antimony compounds such as antimony trioxide; and the like.
Content of the flame retardant in the resin composition which concerns on this embodiment is 1-1000 mass parts with respect to 100 mass parts of cyclic olefin copolymers (A), Preferably it is 10-500 mass parts.

Although it does not specifically limit as an inorganic filler, For example, metal hydroxide type fillers, such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide; silica balloon, alumina, iron oxide, tin oxide, beryllium oxide, barium ferrite, Metal oxide fillers such as strontium ferrite, magnesium oxide, titanium dioxide, zinc oxide, and silicon dioxide (silica); metal chloride fillers such as sodium chloride and calcium chloride; metal sulfates such as sodium sulfate and sodium hydrogen sulfate Salt fillers; Metal nitrate fillers such as sodium nitrate and calcium nitrate; Metal phosphate fillers such as sodium hydrogen phosphate and sodium dihydrogen phosphate; Calcium titanate, strontium titanate, barium titanate, etc. Metal titanate fillers; sodium carbonate, carbonate Metal carbonate fillers such as Lucium, Magnesium carbonate, Sodium bicarbonate; Carbide fillers such as boron carbide and silicon carbide; Nitride fillers such as boron nitride, aluminum nitride and silicon nitride; Aluminum, nickel, magnesium Metal particle fillers such as copper, zinc, iron, gold, silver, lead, tungsten; silicate fillers such as talc, clay, montmorillonite, calcium silicate, glass, glass balloon mica, kaolin, fly ash Glass powder; carbon particles such as carbon black, graphite, activated carbon, carbon balloon; and the like.
Although it does not specifically limit as an organic filler, For example, compound particles, such as wood flour, starch, an organic pigment, polystyrene, nylon, polyolefins, such as polyethylene and a polypropylene, vinyl chloride, and a waste plastic.
The content of the inorganic filler and the organic filler in the resin composition according to the present embodiment is, for example, 1 to 1000 parts by mass, preferably 10 to 500 parts by mass with respect to 100 parts by mass of the cyclic olefin copolymer (A). Part.

<Method for preparing resin composition>
The method for preparing the resin composition according to this embodiment can be prepared by mixing the cyclic olefin copolymer (A), the crosslinking agent (B), and other components as required. As the mixing method, a melt blending method using an extruder or the like, or a suitable solvent such as a saturated hydrocarbon such as heptane, hexane, decane or cyclohexane; an aromatic hydrocarbon such as toluene, benzene or xylene or the like A solution blending method performed by dispersing can be employed.

[varnish]
The resin composition according to this embodiment can be made into a varnish by mixing with a solvent. The solvent for preparing the varnish is not particularly limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (A). Examples of the solvent preferably used include, for example, methanol, ethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, cyclohexane, toluene, m-xylene, p-xylene, mixed xylene, mesitylene, ethylbenzene, chlorobenzene, o-di Examples include chlorobenzene, fluorobenzene, trifluoromethylbenzene, diethyl ether, tetrahydrofuran, dioxane and the like. More preferred are toluene, m-xylene, p-xylene and mixed xylene. These solvents may be used alone or in combination of two or more.

  In the present embodiment, the varnish may be prepared by any method, but usually includes a step of mixing the resin composition and a solvent. About mixing of each component, there is no restriction | limiting in the order, It can implement by any systems, such as a package or a division | segmentation. There is no restriction | limiting also as an apparatus which prepares a varnish, The apparatus of a batch type or a continuous type which can be stirred and mixed can be used. The temperature for preparing the varnish can be arbitrarily selected in the range from room temperature to the boiling point of the solvent.

[Prepreg]
The prepreg according to the present embodiment is formed by combining the resin composition according to the present embodiment and a sheet-like fiber base material.
The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, the method of impregnating a sheet-like fiber base material with the varnish mentioned above and obtaining an impregnated body, and the method of heating the obtained impregnated body and drying the solvent contained in the said varnish are mentioned.
The impregnation of the varnish into the sheet-like fiber base material is performed by, for example, applying a predetermined amount of varnish by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating. It can apply | coat to a fiber-like base material, and can superpose a protective film on it as needed, and can carry out by pressing with a roller etc. from an upper side.
In addition, the step of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but for example, the batch-type drying is performed in an air or nitrogen by a blast dryer, or the heating furnace is operated in a continuous process. The method of drying by passing, etc. can be mentioned.
In this embodiment, after impregnating a sheet-like fiber base material with a varnish, the obtained impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish is evaporated and a prepreg is obtained.

Although it does not specifically limit as a fiber which comprises the sheet-like fiber base material which concerns on this embodiment, For example, organic fibers, such as PET (polyethylene terephthalate) fiber, an aramid fiber, a polyamide (nylon) fiber, a liquid crystal polyester fiber; Glass fiber, And inorganic fibers such as carbon fiber, alumina fiber, tungsten fiber, molybdenum fiber, titanium fiber, steel fiber, boron fiber, silicon carbide fiber, and silica fiber. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, H glass, and T glass can be suitably used.
The impregnation of the sheet-like fiber base material with the varnish is performed, for example, by dipping and coating. The impregnation may be repeated a plurality of times as necessary.
These sheet-like fiber base materials can be used alone or in combination of two or more, and the amount used is appropriately selected as desired. For example, 10 to 90% by mass, preferably 20% in the prepreg. It is -80 mass%, More preferably, it is the range of 30-70 mass%. Within this range, the dielectric properties and mechanical strength of the obtained insulating layer are highly balanced, which is preferable.

  Although the thickness of the prepreg which concerns on this embodiment is suitably selected according to a use purpose, it is 0.001-10 mm, for example, Preferably it is 0.005-1 mm, More preferably, it is 0.01-0. 5 mm. Within this range, the shapeability at the time of lamination and the properties such as mechanical strength and toughness of the insulating layer obtained by curing are sufficiently exhibited, which is preferable.

[Metal-clad laminate]
The prepreg according to the present embodiment may be a metal-clad laminate by laminating a metal foil on at least one surface and heat-curing with a laminating press or the like.
Examples of the metal foil include copper foil, aluminum foil, nickel foil, gold foil, silver foil, and stainless steel foil.
Various known methods can be applied to the method for producing the metal-clad laminate of this embodiment.
For example, a metal-clad laminate can be produced by laminating a metal foil on the prepreg according to the present embodiment and, if necessary, heat curing with a press or the like.

Since the metal-clad laminate according to the present embodiment uses the resin composition according to the present embodiment, the metal-clad laminate is excellent in solder heat resistance while satisfying dielectric properties in a high-frequency region suitable for a printed wiring board. Yes.
Therefore, the metal-clad laminate according to this embodiment can be suitably used as a material for an insulating layer of a printed wiring board.

[Printed wiring board]
As described above, the prepreg according to the present embodiment is excellent in the performance balance between dielectric properties and solder heat resistance, and thus can be suitably used for a printed wiring board.
As a method for producing a printed wiring board, generally known methods can be adopted and are not particularly limited. For example, the prepreg produced by the above-described method is heat-cured by a lamination press or the like to form an insulating layer. Next, a conductor layer is laminated on the obtained insulating layer by a known method to produce a laminate. Then, a printed wiring board can be obtained by carrying out circuit processing etc. of the conductor layer in this laminated body.

  As a metal used as a conductor layer, metals, such as copper, aluminum, nickel, gold | metal | money, silver, stainless steel, can be used. As a method of forming the conductor layer, in addition to the method of heat-sealing the metal to the insulating layer using a foil or the like, lamination is performed by using an adhesive, or by sputtering, vapor deposition, plating, or the like. It can be manufactured by a forming method. As an aspect of the printed wiring board, either a single-sided board or a double-sided board may be used.

Such a printed wiring board can be used as an electronic device by mounting electronic components such as semiconductor elements. The electronic device can be manufactured based on known information.
Examples of such electronic devices include ICT infrastructure devices such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, radio base station antennas, millimeter wave antennas, and RFID antennas; mobile phones , Communication devices such as smartphones, PHS, PDAs, tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, digital media players; electronic control system devices, in-vehicle communication devices, cars In-vehicle electronic devices such as navigation devices, millimeter wave radars, and in-vehicle camera modules; semiconductor test devices, high-frequency measurement devices, and the like.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a scope that can achieve the object of the present invention are included in the present invention.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not restrict | limited at all by this.

  The laminates obtained in Examples and Comparative Examples were evaluated by the method described below.

(1) Evaluation of heat resistance The storage elastic modulus (E ') at 250 ° C was measured as an index of heat resistance. The measurement was performed using RSA-III (TA-Instruments) under a nitrogen atmosphere, scanning at a frequency of 1 Hz, a strain of 0.1, and a range from 25 ° C. to 300 ° C. at a temperature rising rate of 3 ° C./min. For the measurement, a test piece cut out to a length of 50 mm and a width of 5 mm from the obtained laminate was used. The heat resistance of the resin composition was evaluated according to the following criteria.
A: Storage elastic modulus (E ′) at 250 ° C. is 1 × 10 ⁷ Pa or more ○: Storage elastic modulus (E ′) at 250 ° C. is 1 × 10 ⁶ Pa or more and less than 1 × 10 ⁷ Pa ×: Storage at 250 ° C. Elastic modulus (E ′) is less than 1 × 10 ⁶ Pa Here, if the storage elastic modulus (E ′) is 1 × 10 ⁶ Pa or more, it has been confirmed that no appearance abnormality occurs in the solder heat resistance test.

(2) Solder heat resistance evaluation The state after dipping the copper clad laminate in a solder bath at 288 ° C. for 20 seconds was observed. The solder heat resistance of the copper clad laminate was evaluated according to the following criteria.
○: Neither deformation nor blistering occurred ×: At least one of deformation and blistering occurred

(3) Dielectric loss tangent evaluation The dielectric loss tangent of the laminated body at 12 GHz was measured by the cylindrical cavity resonator method. Specifically, the dielectric loss tangent of the laminate at 12 GHz was measured using a network analyzer (8510B manufactured by YHP), a synthesized sweeper (8340B manufactured by YHP), and a test set (8515A).

(4) Workability evaluation The laminateability when a copper-clad laminate was produced by a vacuum press was evaluated.
○: Can be laminated at 280 ° C or less ×: Cannot be laminated at 280 ° C or less

  The following raw materials were used for the experiment.

Transition metal compound (1): CpTiCl ₂ (N = C ^t Bu ₂ )
J. et al. Am. Chem. Soc. 2000, 122, 5499-5509. It was synthesized by the method described in 1.

MAO (Nippon Alkyl Aluminum Co., Ltd.)
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (Mitsui Chemicals, Inc.)
Cross-linking agent 1: 2,3-dimethyl-2,3-diphenylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.)
Cross-linking agent 2: Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D)

(Cyclic olefin copolymer (A))
Cyclic olefin copolymer (A-1): 1-octene (hereinafter also referred to as C8) and tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene (hereinafter also referred to as TD) (C8 / TD = 34/66 (molar ratio), Tg: 246 ° C.)
Cyclic olefin copolymer (A-2): 1-hexene (hereinafter also referred to as C6) and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (C6 / TD = 46/54 (molar ratio), Tg: 220 ° C.)
Cyclic olefin copolymer (A-3): 1-hexene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (C6 / TD = 65/35 (molar ratio), Tg: 188 ° C.)
Cyclic olefin copolymer (A-4): 1-hexene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (C6 / TD = 77/23 (molar ratio), Tg: 151 ° C.)
Cyclic olefin copolymer (A-5): A copolymer composed of ethylene and bicyclo [2.2.1] -2-heptene (Product name: TOPAS 6013S-04, manufactured by Polyplastics, Tg: 138 ° C.)
Cyclic olefin copolymer (A-6): 1-hexene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (C6 / TD = 32/68 (molar ratio), Tg: 284 ° C.)

[Synthesis Example 1: Synthesis of cyclic olefin copolymer (A-1)]
A glass reactor sufficiently purged with nitrogen was charged with 40 mL of toluene, and the liquid phase and the gas phase were saturated with nitrogen at a flow rate of 30 L / h. Subsequently, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (TD) 20.0 mL, 1-octene 5.5 mL as an α-olefin, and 10 mmol of methylaluminoxane (MAO) in terms of aluminum atom were added. 0.010 mmol of a transition metal compound (1) dissolved in toluene was added to initiate polymerization. After continuing the polymerization at 25 ° C. for 15 minutes, the polymerization was stopped by adding isobutyl alcohol. The reaction product was put into a mixed solvent of acetone / methanol (each 500 ml) to which 0.5 mL of concentrated hydrochloric acid was added to precipitate the whole amount of the polymer, and after stirring, it was filtered through a glass filter. The polymer was dried under reduced pressure at 130 ° C. for 10 hours to obtain a TD / 1-octene copolymer. The monomer composition in the polymer determined by NMR was TD 66 mol%, 1-octene 34 mol%, and the glass transition temperature measured by DSC was 246 ° C.
Here, the NMR analysis method followed the method described in Macromolecules 2016, 49, 59-70.

[Synthesis Example 2: Synthesis of cyclic olefin copolymer (A-2)]
A TD / 1-hexene copolymer was synthesized in the same manner as in Synthesis Example 1, except that the α-olefin was changed to 14.0 mL of 1-hexene. The monomer composition in the polymer determined by NMR was TD 54 mol%, 1-hexene 46 mol%, and the glass transition temperature measured by DSC was 220 ° C.

[Synthesis Example 3: Synthesis of Cyclic Olefin Copolymer (A-3)]
A TD / 1-hexene copolymer was synthesized in the same manner as in Synthesis Example 1 except that the α-olefin was changed to 28.2 mL of 1-hexene. The monomer composition in the polymer determined by NMR was TD 35 mol%, 1-hexene 65 mol%, and the glass transition temperature measured by DSC was 188 ° C.

[Synthesis Example 4: Synthesis of cyclic olefin copolymer (A-4)]
A TD / 1-hexene copolymer was synthesized in the same manner as in Synthesis Example 1, except that 1-hexene was changed to 55.0 mL. The monomer composition in the polymer determined by NMR was TD 23 mol%, 1-hexene 77 mol%, and the glass transition temperature measured by DSC was 151 ° C.

[Synthesis Example 5: Synthesis of cyclic olefin copolymer (A-6)]
A TD / 1-hexene copolymer was synthesized in the same manner as in Synthesis Example 1, except that the α-olefin was changed to 3.7 mL of 1-hexene. The monomer composition in the polymer determined by NMR was TD68 mol%, 1-hexene 32 mol%, and the glass transition temperature measured by DSC was 284 ° C.

(Crosslinking aid (C))
Crosslinking aid 1: divinylbenzene

[Example 1]
(Preparation of varnish)
The cyclic olefin copolymer (A-1) and the crosslinking agent 1 are added to toluene in the blending ratio shown in Table 1 (the numerical values in the table indicate parts by mass) and mixed to form a varnish-like resin composition. Was prepared.

(Film casting)
The obtained varnish-like resin composition was applied onto a release-treated PET film at a speed of 10 mm / second, and then dried at 120 ° C. for 10 minutes in a blower dryer under a nitrogen stream. A film was prepared by peeling the film from the PET film.

(Production of laminate)
Eight films cut into 150 mm squares were stacked, and a laminate was produced by heating at a pressure of 3.5 MPa and 280 ° C. for 60 minutes with a vacuum press. The heat resistance evaluation of the obtained laminated body was performed. The obtained results are shown in Table 1.
Moreover, it was 0.0011 as a result of measuring the dielectric loss tangent of a laminated body.

(Preparation of copper-clad laminate)
A copper-clad laminate to which copper foil is bonded by stacking eight films cut into 150 mm squares, and further copper foil on both sides thereof, and heating at a pressure of 3.5 MPa and 280 ° C. for 60 minutes with a vacuum press machine. Produced. The obtained copper-clad laminate was evaluated for workability and solder heat resistance. The obtained results are shown in Table 1.

[Examples 2-3 and Comparative Example 1]
Except having changed the mixture ratio of each component into the mixture ratio of Table 1, it carried out similarly to Example 1, and produced the laminated body and the copper clad laminated body, respectively, and performed each evaluation, respectively.
The obtained results are shown in Table 1.

[Example 4]
A laminate and a copper-clad laminate were produced in the same manner as in Example 1 except that the blending ratio of each component was changed to the blending ratio shown in Table 1 and the pressing conditions were set to pressure 3.5 MPa, 250 ° C., 90 minutes. Then, each evaluation was performed.
The obtained results are shown in Table 1.

[Example 5 and Comparative Example 2]
The laminated body and the copper clad laminated body were respectively the same as in Example 1 except that the blending ratio of each component was changed to the blending ratio shown in Table 1 and the pressing conditions were set to pressure 3.5 MPa, 200 ° C., 120 minutes. It produced and each evaluation was performed, respectively.
The obtained results are shown in Table 1.

[Comparative Example 3]
The laminated body and the copper clad laminated body were respectively the same as in Example 1 except that the blending ratio of each component was changed to the blending ratio shown in Table 1 and the pressing conditions were set to pressure 3.5 MPa, 280 ° C., 60 minutes. Produced.

As can be seen from Table 1, it was found that the copper clad laminates of Examples 1 to 5 were excellent in solder heat resistance and workability. Further, the dielectric loss tangent measurement result of Example 1 shows that the dielectric characteristics in the high frequency region are good.
On the other hand, the film of the comparative example 1 which does not contain a crosslinking agent (B) and the film of the comparative example 2 using the cyclic olefin copolymer whose glass transition temperature is less than 150 degreeC were respectively inferior to solder heat resistance. Moreover, the film of the comparative example 3 using the cyclic olefin copolymer whose glass transition temperature exceeds 250 degreeC cannot be laminated | stacked at 280 degrees C or less, and was inferior to workability.

Claims (11)

A resin composition comprising a cyclic olefin copolymer (A) having a glass transition temperature of 150 ° C. or higher and lower than 250 ° C., and a crosslinking agent (B),
The resin composition whose ratio ((A) / (B)) of content of the said cyclic olefin copolymer (A) with respect to content of the said crosslinking agent (B) in the said resin composition is 10-200. The resin composition according to claim 1,
The cyclic olefin copolymer (A) is:
A repeating unit (a) derived from at least one α-olefin represented by the following general formula (I);
At least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV) The resin composition containing the repeating unit (b) derived from.

(In the general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. -20 aromatic hydrocarbon groups, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring.)

(In the general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same as or different from each other, An aliphatic hydrocarbon group which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group; And the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. And when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .) In the resin composition according to claim 1 or 2,
When the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%,
At least one non-conjugated selected from the group consisting of a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating unit represented by the following general formula (VII) The resin composition whose content of the repeating unit (c) derived from a diene olefin is 0.05 mol% or less.

(In the general formula (V), R ²⁰¹ to R ²⁰⁶ may be the same as or different from each other, and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is one having 1 to 20 carbon atoms. (It is a linear or branched hydrocarbon group and may contain a double bond and / or a triple bond.)

(In the general formula (VI), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. An aromatic hydrocarbon group of ˜20, R ¹⁰² and R ¹⁰³ may be the same or different from each other, are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁷⁵ and R ⁷⁶ are bonded to each other And may form a monocyclic or polycyclic ring.)

(In the general formula (VII), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. However, they may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ˜20 aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. And may form a monocyclic or polycyclic ring.) In the resin composition according to claim 2 or 3,
The repeating unit (a) derived from the α-olefin in the cyclic olefin copolymer (A) is a linear hydrocarbon group having 2 to 10 carbon atoms and R ³⁰⁰ in the general formula (I). A resin composition containing a certain repeating unit. In the resin composition as described in any one of Claims 2 thru | or 4,
The cyclic olefin-derived repeating unit (b) in the cyclic olefin copolymer (A) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . The resin composition which is a repeating unit derived from at least 1 type of compound chosen from 1 ^<7 >, ¹⁰ ] -3-dodecene. In the resin composition as described in any one of Claims 2 thru | or 5,
When the total number of repeating units contained in the cyclic olefin copolymer (A) is 100 mol%,
The resin composition whose content of the repeating unit (b) derived from the cyclic olefin is 10 mol% or more and 90 mol% or less. In the resin composition as described in any one of Claims 1 thru | or 6,
The resin composition which further contains the crosslinking adjuvant (C) which has a carbon-carbon unsaturated bond.   A prepreg comprising the resin composition according to any one of claims 1 to 7 and a sheet-like fiber base material.   A metal-clad laminate obtained by laminating the prepreg according to claim 8 and a metal foil.   A printed wiring board comprising an insulating layer formed by the prepreg according to claim 8 and a conductor layer provided on the insulating layer.   The electronic device provided with the printed wiring board of Claim 10.