JP2017125174A - Polyphenylene ether resin composition, cured product, dry film, film, prepreg, metal-clad laminate, printed wiring board and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition which makes it possible to obtain a cured product that satisfies dielectric properties in a high frequency region suitable for a printed wiring board while having excellent heat resistance and heat stability.SOLUTION: A polyphenylene ether resin composition comprises polyphenylene ether (A), and a cyclic olefin (co) polymer (B). The ratio between a content of the polyphenylene ether (A) to a content of the cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition, ((A)/(B)), is more than 5 and 50 or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyphenylene ether resin composition, a cured product, a dry film, a film, 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, printed wiring board materials having a low dielectric loss tangent are required in order to reduce transmission loss at high frequencies to the limit.

  Examples of the insulating resin material used for such a printed wiring board include a resin composition containing polyphenylene ether described in Patent Document 1.

  Patent Document 1 (International Publication No. 2014/203511) includes (A) a modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond and (B) a carbon-carbon unsaturated double bond. The crosslinking agent which is a component (B) contains 50 to 100% by mass of (B-1) divinylbenzene and (B-2) polybutadiene, and contains component (A) and component (B). The content ratio is mass ratio, the component (A): component (B) = 65: 35 to 95: 5, and the content ratio of the component (B-1) and the component (B-2) is mass ratio, There is described a polyphenylene ether resin composition characterized in that component (B-1): component (B-2) = 1: 100 to 1.5: 1.

International Publication No. 2014/203511

In recent years, the required characteristics of insulating layers used for printed wiring boards have further increased, and there is a demand for insulating resin materials having heat resistance, dielectric characteristics and thermal stability.
According to the study by the present inventors, the conventional polyphenylene ether resin composition has room for improvement in terms of improving the dielectric properties, heat resistance, and thermal stability of the resulting cured product in a balanced manner. Became clear.

  The present invention has been made in view of the above circumstances, and is a polyphenylene ether capable of obtaining a cured product excellent in heat resistance and thermal stability while satisfying dielectric characteristics in a high frequency region suitable for a printed wiring board. A resin composition is provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed polyphenylene ether and a cyclic olefin (co) polymer at a specific ratio, thereby satisfying heat resistance and thermal stability, while maintaining high frequency. The present inventors have found that the dielectric characteristics in the region are improved and completed the present invention.

  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［２］に記載のポリフェニレンエーテル樹脂組成物において、
上記環状オレフィン（共）重合体（Ｂ）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ポリフェニレンエーテル樹脂組成物。
［４］
上記［２］または［３］に記載のポリフェニレンエーテル樹脂組成物において、
上記環状オレフィン（共）重合体（Ｂ）が、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）をさらに含有するポリフェニレンエーテル樹脂組成物。

（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。）
［５］
上記［４］に記載のポリフェニレンエーテル樹脂組成物において、
上記環状オレフィン（共）重合体（Ｂ）中の上記非共役ジエン系オレフィン由来の繰り返し単位（ｃ）が、上記一般式（ＶＩＩ）で表される環状非共役ジエン由来の繰り返し単位を含むポリフェニレンエーテル樹脂組成物。
［６］
上記［４］または［５］に記載のポリフェニレンエーテル樹脂組成物において、
上記環状オレフィン（共）重合体（Ｂ）中の上記非共役ジエン系オレフィン由来の繰り返し単位（ｃ）が５−ビニル−２−ノルボルネンおよび８−ビニル−９−メチルテトラシクロ［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１種の化合物に由来する繰り返し単位であるポリフェニレンエーテル樹脂組成物。
［７］
上記［１］乃至［６］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物において、
上記環状オレフィン（共）重合体（Ｂ）の、１３５℃のデカリン中での極限粘度［η］が０．０１ｄｌ／ｇ以上１．０ｄｌ／ｇ以下であるポリフェニレンエーテル樹脂組成物。
［８］
上記［１］乃至［７］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物において、
上記ポリフェニレンエーテル（Ａ）が、炭素−炭素不飽和結合を有する置換基により変性された変性ポリフェニレンエーテルを含むポリフェニレンエーテル樹脂組成物。
［９］
上記［１］乃至［８］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物において、
架橋助剤（Ｄ）をさらに含むポリフェニレンエーテル樹脂組成物。
［１０］
上記［９］に記載のポリフェニレンエーテル樹脂組成物において、
当該ポリフェニレンエーテル樹脂組成物中の上記ポリフェニレンエーテル（Ａ）の含有量を１００質量部としたとき、
上記環状オレフィン（共）重合体（Ｂ）の含有量が２質量部以上２０質量部未満であり、
上記架橋助剤（Ｄ）の含有量が５質量部以上５０質量部以下であるポリフェニレンエーテル樹脂組成物。
［１１］
上記［１］乃至［１０］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物において、
上記ポリフェニレンエーテル（Ａ）の数平均分子量が５００以上７０００以下であるポリフェニレンエーテル樹脂組成物。
［１２］
上記［１］乃至［１１］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物において、
上記ポリフェニレンエーテル（Ａ）と上記環状オレフィン（共）重合体（Ｂ）とを相溶化させる相溶化剤（Ｃ）をさらに含有するポリフェニレンエーテル樹脂組成物。
［１３］
上記［１２］に記載のポリフェニレンエーテル樹脂組成物において、
上記相溶化剤（Ｃ）が変性ポリオレフィンおよび変性エラストマーから選択される少なくとも一種を含むポリフェニレンエーテル樹脂組成物。
［１４］
上記［１２］または［１３］に記載のポリフェニレンエーテル樹脂組成物において、
上記相溶化剤（Ｃ）の含有量が、当該ポリフェニレンエーテル樹脂組成物中の上記ポリフェニレンエーテル（Ａ）を１００質量部としたとき、０．１質量部以上１０質量部以下であるポリフェニレンエーテル樹脂組成物。
［１５］
上記［１］乃至［１４］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物を硬化してなる硬化物。
［１６］
上記［１］乃至［１４］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物からなるドライフィルム。
［１７］
上記［１６］に記載のドライフィルムを硬化してなるフィルム。
［１８］
上記［１］乃至［１４］のいずれか一つに記載のポリフェニレンエーテル樹脂組成物とシート状繊維基材とを含むプリプレグ。
［１９］
上記［１６］に記載のドライフィルム、上記［１７］に記載のフィルム、および上記［１８］に記載のプリプレグから選択される少なくとも一種と、金属箔と、を積層してなる金属張積層板。
［２０］
上記［１６］に記載のドライフィルム、上記［１７］に記載のフィルム、および上記［１８］に記載のプリプレグから選択される少なくとも一種により形成された電気絶縁層と、上記電気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。
［２１］
上記［２０］に記載のプリント配線基板を備えた電子機器。 [1]
A polyphenylene ether resin composition comprising a polyphenylene ether (A) and a cyclic olefin (co) polymer (B),
The ratio of the content of the polyphenylene ether (A) to the content of the cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition ((A) / (B)) is more than 5 and 50 or less. Polyphenylene ether resin composition.
[2]
In the polyphenylene ether resin composition according to the above [1],
The cyclic olefin (co) polymer (B) is
A repeating unit (a) derived from at least one 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) A polyphenylene ether resin composition comprising a repeating unit (b) derived from the same.

(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 polyphenylene ether resin composition according to the above [2],
The repeating unit (b) derived from the cyclic olefin in the cyclic olefin (co) polymer (B) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5. . A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from 1 ^7,10 ] -3-dodecene.
[4]
In the polyphenylene ether resin composition according to the above [2] or [3],
The cyclic olefin (co) polymer (B) is a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating represented by the following general formula (VII) A polyphenylene ether resin composition further comprising a repeating unit (c) derived from at least one non-conjugated diene-based olefin selected from the group consisting of units.

(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.)
[5]
In the polyphenylene ether resin composition according to the above [4],
The polyphenylene ether in which the repeating unit (c) derived from the non-conjugated diene olefin in the cyclic olefin (co) polymer (B) includes a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (VII) Resin composition.
[6]
In the polyphenylene ether resin composition according to the above [4] or [5],
The repeating unit (c) derived from the non-conjugated diene olefin in the cyclic olefin (co) polymer (B) is 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo [4.4.0. .1 ^2,5 . A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from 1 ^7,10 ] -3-dodecene.
[7]
In the polyphenylene ether resin composition according to any one of the above [1] to [6],
A polyphenylene ether resin composition having an intrinsic viscosity [η] in decalin at 135 ° C. of 0.01 to 1.0 dl / g of the cyclic olefin (co) polymer (B).
[8]
In the polyphenylene ether resin composition according to any one of the above [1] to [7],
A polyphenylene ether resin composition comprising a modified polyphenylene ether in which the polyphenylene ether (A) is modified with a substituent having a carbon-carbon unsaturated bond.
[9]
In the polyphenylene ether resin composition according to any one of the above [1] to [8],
A polyphenylene ether resin composition further comprising a crosslinking aid (D).
[10]
In the polyphenylene ether resin composition according to the above [9],
When the content of the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by mass,
The content of the cyclic olefin (co) polymer (B) is 2 parts by mass or more and less than 20 parts by mass,
The polyphenylene ether resin composition whose content of the said crosslinking adjuvant (D) is 5 to 50 mass parts.
[11]
In the polyphenylene ether resin composition according to any one of the above [1] to [10],
A polyphenylene ether resin composition wherein the polyphenylene ether (A) has a number average molecular weight of 500 or more and 7,000 or less.
[12]
In the polyphenylene ether resin composition according to any one of the above [1] to [11],
A polyphenylene ether resin composition further comprising a compatibilizer (C) for compatibilizing the polyphenylene ether (A) and the cyclic olefin (co) polymer (B).
[13]
In the polyphenylene ether resin composition according to the above [12],
A polyphenylene ether resin composition comprising the compatibilizer (C) containing at least one selected from a modified polyolefin and a modified elastomer.
[14]
In the polyphenylene ether resin composition according to the above [12] or [13],
A polyphenylene ether resin composition in which the content of the compatibilizer (C) is 0.1 parts by mass or more and 10 parts by mass or less when the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by mass. object.
[15]
Hardened | cured material formed by hardening | curing the polyphenylene ether resin composition as described in any one of said [1] thru | or [14].
[16]
A dry film comprising the polyphenylene ether resin composition according to any one of [1] to [14].
[17]
The film formed by hardening | curing the dry film as described in said [16].
[18]
A prepreg comprising the polyphenylene ether resin composition according to any one of the above [1] to [14] and a sheet-like fiber base material.
[19]
A metal-clad laminate obtained by laminating at least one selected from the dry film according to [16], the film according to [17], and the prepreg according to [18], and a metal foil.
[20]
An electrical insulating layer formed of at least one selected from the dry film described in [16] above, the film described in [17] above, and the prepreg described in [18] above, and provided on the electrical insulating layer Printed circuit board comprising the conductive layer formed.
[21]
Electronic equipment comprising the printed wiring board according to [20] above.

  According to the present invention, it is possible to provide a polyphenylene ether resin composition capable of obtaining a cured product excellent in heat resistance and thermal stability while satisfying dielectric characteristics in a high frequency region suitable for a printed wiring board. it can.

  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.

[Polyphenylene ether resin composition]
First, the polyphenylene ether resin composition of the embodiment according to the present invention will be described.
The polyphenylene ether resin composition according to this embodiment includes polyphenylene ether (A) and a cyclic olefin (co) polymer (B). And ratio ((A) / (B)) of content of polyphenylene ether (A) to content of cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition is more than 5 and 50 or less. , Preferably it is 5.2 or more and 20 or less, More preferably, it is 5.2 or more and 10 or less.
When (A) / (B) is greater than or equal to the above lower limit value or exceeding, the obtained cured product can be improved in thermal stability while satisfying good dielectric properties and heat resistance. In addition, when (A) / (B) is not more than the above upper limit value, the obtained cured product can improve the dielectric properties while satisfying good thermal stability and heat resistance.
From the above, when (A) / (B) is within the above range, a cured product excellent in heat resistance and thermal stability can be obtained while satisfying dielectric characteristics in a high frequency region suitable for a printed wiring board. Is possible.

In addition, the total content of polyphenylene ether (A) and cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition according to this embodiment is the dielectric properties, heat resistance, and thermal stability of the resulting cured product. From the viewpoint of further improving the performance balance of the property, when the total of the polyphenylene ether resin composition is 100% by mass, it is preferably 20% by mass to 100% by mass, and more preferably 30% by mass to 99% by mass. It is below, More preferably, it is 40 to 97 mass%.
Hereinafter, each component will be specifically described.

[Polyphenylene ether (A)]
As the polyphenylene ether (A) according to this embodiment, for example, at least one selected from unmodified polyphenylene ether and modified polyphenylene ether can be used.
The modified polyphenylene ether is not particularly limited, and for example, those described in paragraphs 0018 to 0061 of International Publication No. 2014/203511 can be used.
More specifically, it is as follows.

The modified polyphenylene ether according to this embodiment is not particularly limited, but is preferably a modified polyphenylene ether that has been terminally modified with a substituent having a carbon-carbon unsaturated bond.
Although it does not specifically limit as a substituent which has a carbon-carbon unsaturated bond, For example, the substituent shown by following formula (1) is mentioned.

上記式（１）中、ｎは０〜１０の整数を示し、Ｚはアリーレン基を示し、Ｒ^１〜Ｒ^３は独立して水素原子またはアルキル基を示す。
ここで、上記式（１）においてｎ＝０の場合は、Ｚがポリフェニレンエーテルの末端に直接結合しているものを示す。また、Ｚのアリーレン基としては、例えば、フェニレン基等の単環芳香族基やナフタレン環等の多環芳香族基が挙げられ、芳香族環に結合する水素原子がアルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基等の官能基で置換された誘導体も含む。

In the above formula (1), n represents an integer of 0, Z represents an arylene ^group, R 1 to R ³ represents a hydrogen atom or an alkyl group independently.
Here, in the above formula (1), when n = 0, it indicates that Z is directly bonded to the terminal of the polyphenylene ether. Examples of the arylene group for Z include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group such as a naphthalene ring, and a hydrogen atom bonded to the aromatic ring is an alkenyl group, an alkynyl group, a formyl group. And derivatives substituted with a functional group such as a group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.

  Examples of the functional group represented by the above formula (1) include a functional group containing a vinylbenzyl group. More specifically, at least one substituent selected from the following formula (2) or formula (3) is exemplified.

  As another substituent which has the said carbon-carbon unsaturated bond, the (meth) acrylate group shown by following formula (4) is mentioned, for example.

上記式（４）中、Ｒ^４は水素原子またはアルキル基を示す。

In the above formula (4), R ⁴ represents a hydrogen atom or an alkyl group.

  The number average molecular weight of the polyphenylene ether (A) according to the present embodiment is not particularly limited, but is 500 or more and 7000 or less from the viewpoint of improving the balance of dielectric properties, adhesion, and heat resistance of the obtained cured product. Is more preferably 1000 or more and 5000 or less, and still more preferably 1000 or more and 3000 or less. Here, the number average molecular weight is a value measured using gel permeation chromatography (GPC).

  Moreover, the polyphenylene ether (A) according to the present embodiment has a polyphenylene ether chain in the molecule, and preferably has, for example, a repeating unit represented by the following formula (5) in the molecule. .

上記式（５）において、ｍは１〜５０を示す。また、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立し、それぞれ同一の基であっても、異なる基であってもよい。また、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、水素原子、アルキル基、アルケニル基、アルキニル基、ホルミル基、アルキルカルボニル基、アルケニルカルボニル基、又はアルキニルカルボニル基を示す。これらの中でも、水素原子及びアルキル基が好ましい。

In said formula (5), m shows 1-50. R ⁵ , R ⁶ , R ⁷ and R ⁸ are independent of each other and may be the same group or different groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferable.

Although the said alkyl group is not specifically limited, For example, a C1-C18 alkyl group is preferable and a C1-C10 alkyl group is more preferable. More specifically, examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
Although an alkenyl group is not specifically limited, For example, a C2-C18 alkenyl group is preferable and a C2-C10 alkenyl group is more preferable. More specifically, a vinyl group, an allyl group, a 3-butenyl group, and the like can be given.
Although an alkynyl group is not specifically limited, For example, a C2-C18 alkynyl group is preferable and a C2-C10 alkynyl group is more preferable. More specifically, an ethynyl group, a prop-2-yn-1-yl group (propargyl group), etc. are mentioned.

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. More specifically, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group, and the like can be given.
The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. More specifically, an acryloyl group, a methacryloyl group, a crotonoyl group, etc. are mentioned.
The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. More specifically, a propioroyl group etc. are mentioned.

  In addition, when the modified polyphenylene ether has a repeating unit represented by the above formula (5) in the molecule, m is a numerical value such that the number average molecular weight of the modified polyphenylene ether falls within the range as described above. Preferably there is. Specifically, it is preferably 1 to 50.

  The method for synthesizing the modified polyphenylene ether according to the present embodiment is not particularly limited as long as it can synthesize modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated bond. Examples thereof include a method of reacting a polyphenylene ether in which a hydrogen atom of a terminal phenolic hydroxyl group is substituted with an alkali metal atom such as sodium or potassium with a compound represented by the following formula (6).

In the above formula (6), similarly to the above formula (1), n represents an integer of 0, Z represents an arylene ^group, R 1 to R ³ represents a hydrogen atom or an alkyl group independently. X represents a halogen atom, and specific examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Among these, a chlorine atom is preferable.

  Moreover, the compound represented by the said Formula (6) is although it does not specifically limit, For example, p-chloromethyl styrene and m-chloromethyl styrene are preferable.

  Moreover, the compound represented by the said Formula (6) may use what was illustrated above independently, and may be used in combination of 2 or more type.

  The polyphenylene ether as a raw material is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether. Specifically, a polyarylene ether copolymer composed of 2,6-dimethylphenol and at least one of a bifunctional phenol and a trifunctional phenol, poly (2,6-dimethyl-1,4-phenylene oxide), etc. And those containing polyphenylene ether as a main component. More specifically, such polyphenylene ether includes, for example, polyphenylene ether having a structure represented by the following formula (7).

  In the above formula (7), for s and t, for example, the total value of s and t is preferably 1 to 30. Moreover, it is preferable that s is 0-20, and it is preferable that t is 0-20. That is, s represents 0 to 20, t represents 0 to 20, and the sum of s and t preferably represents 1 to 30.

[Cyclic olefin (co) polymer (B)]
The cyclic olefin (co) polymer (B) according to this embodiment is a (co) polymer having a repeating unit derived from a cyclic olefin as an essential constituent unit.
Although the cyclic olefin compound which comprises the cyclic olefin (co) polymer (B) which concerns on this embodiment is not specifically limited, For example, the cyclic olefin monomer of Paragraph 0037-0063 of international publication 2006/0118261 is mentioned, for example. be able to.

  The cyclic olefin (co) polymer (B) according to this embodiment is a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and the following general formula (IV). It is preferable to contain at least one cyclic olefin-derived repeating unit (b) selected from the group consisting of the repeating units represented, and the resulting cured product, prepreg, and printed circuit board have good heat resistance and thermal stability. In view of the ability to further improve the dielectric properties while maintaining the same, or to improve the impregnation of the polyphenylene ether resin composition into the sheet-like fiber base material when preparing the prepreg, it is represented by the following general formula (I) A repeating unit (a) derived from at least one olefin, a repeating unit represented by the following general formula (II), and a repeating unit represented by the following general formula (III): And to the unit and at least one cyclic olefin-derived repeating units selected from the group consisting of repeating units represented by the following general formula (IV) (b), and more preferably contains 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。

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.

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.

  In addition, the cyclic olefin (co) polymer (B) according to the present embodiment has excellent heat resistance (particularly solder heat resistance) while maintaining good dielectric properties and thermal stability of the obtained cured product, prepreg, and printed wiring board. From the viewpoint of further improving the impregnation property into the sheet-like fiber substrate, the repeating unit represented by the following general formula (V), the repeating unit represented by the following general formula (VI), and the following general formula (VII) It is preferable to further contain a repeating unit (c) derived from at least one non-conjugated diene-based olefin selected from the group consisting of repeating units derived from a cyclic non-conjugated diene represented by the following general formula (VII) It is particularly preferable to include a repeating unit.

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 copolymerization raw materials of the cyclic olefin (co) polymer (B) 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。上記一般式（Ｉａ）で表されたオレフィンモノマーとしては、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、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−ヘキセン、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−ヘキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等が挙げられる。優れた耐熱性、機械的特性、誘電特性、および透明性を有する硬化物を得る観点から、これらのなかでも、エチレンとプロピレンが好ましく、エチレンが特に好ましい。上記一般式（Ｉａ）で表されるオレフィンモノマーは２種類以上を用いてもよい。
本実施形態に係る環状オレフィン（共）重合体（Ｂ）中に含まれる、オレフィンモノマー由来の繰り返し単位（ａ）と、環状オレフィンモノマー（ｂ）由来の繰り返し単位（ｂ）と、側鎖部分に架橋性二重結合を有するモノマー（ｃ）由来の繰り返し単位（ｃ）との合計モル数を１００モル％としたとき、オレフィン由来の繰り返し単位（ａ）の割合が、好ましくは４０モル％以上９０モル％以下、より好ましくは４５モル％以上８５モル％以下、さらに好ましくは５０モル％以上８０モル％以下である。

In the general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin monomer represented by the general formula (Ia) include ethylene, propylene, 1-butene, 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, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. Among these, ethylene and propylene are preferable and ethylene is particularly preferable from the viewpoint of obtaining a cured product having excellent heat resistance, mechanical properties, dielectric properties, and transparency. Two or more kinds of olefin monomers represented by the general formula (Ia) may be used.
In the cyclic olefin (co) polymer (B) according to this embodiment, the repeating unit (a) derived from the olefin monomer, the repeating unit (b) derived from the cyclic olefin monomer (b), and the side chain portion When the total number of moles of the repeating unit (c) derived from the monomer (c) having a crosslinkable double bond is 100 mol%, the proportion of the repeating unit (a) derived from the olefin is preferably 40 mol% or more and 90 The mol% or less, more preferably 45 mol% or more and 85 mol% or less, and further preferably 50 mol% or more and 80 mol% or less.

(Cyclic olefin monomer (b))
The cyclic olefin monomer (b), which is one of the copolymerization raw materials of the cyclic olefin (co) polymer (B) according to the present embodiment, is subjected to addition copolymerization to perform the above general formula (II), the above general formula (III), or The repeating unit (b) derived from the cyclic olefin represented by the general 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 a copolymerization component, a cyclic olefin ( Since the solubility of the (co) polymer (B) 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 cured product, and since they do not contain a heterogeneous double bond structure, there is an advantage that the crosslinking can be easily controlled.

  Crosslinkability to the repeating unit (a) derived from the olefin monomer, the repeating unit (b) derived from the cyclic olefin monomer (b), and the side chain portion contained in the cyclic olefin (co) polymer (B) according to this embodiment. When the total number of moles of the repeating unit (c) derived from the monomer (c) having a double bond is 100 mol%, the ratio of the repeating unit (b) derived from the cyclic olefin monomer (b) is preferably 1 mole. % To 50 mol%, more preferably 3 mol% to 45 mol%, and still more preferably 5 mol% to 40 mol%.

(Monomer (c) having a crosslinkable double bond in the side chain portion)
The monomer (c) having a crosslinkable double bond in the side chain portion, which is one of the copolymerization raw materials of the cyclic olefin (co) polymer (B) according to this embodiment, is subjected to addition copolymerization to produce the above general formula (V ), The repeating unit (c) derived from the non-conjugated diene olefin of the general formula (VI) or the general formula (VII). Specifically, the side chain moieties represented by the general formulas (Va), (VIa), and (VIIa) corresponding to the general formula (V), the general formula (VI), and the general formula (VII), respectively, A monomer (c) having a crosslinkable double bond is used.

In the general formula (Va), 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 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.

  Although it does not specifically limit as a linear polyene represented by the said general formula (Va), For example, 1, 4-hexadiene, 3-methyl-1, 4-hexadiene, 4-methyl-1, 4 -Hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene, etc. Can be mentioned. A cyclizable polyene cyclized from a polyene such as 1,3-butadiene and 1,5-hexadiene may also be used.

In the above general formula (VIa), 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 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.

Although it does not specifically limit as a monomer (c) which has a crosslinkable double bond in the side chain part represented by the said general formula (VIa), For example, 5-ethylidene-2-norbornene, 5-n -Propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-ethylidene-6-methyl-2-norbornene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. Of these, 5-ethylidene-2-norbornene is preferred.

In the general formula (VIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 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.

Although it does not specifically limit as a monomer (c) which has a crosslinkable double bond in the side chain part represented by the said general formula (VIIa), For example, it bridge | crosslinks to the side chain part represented by following Chemical formula And a monomer (c) having an ionic double bond. Of these, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

  The cyclic olefin (co) polymer (B) according to the present embodiment includes a repeating unit (c) derived from the monomer (c) having a crosslinkable double bond in the side chain portion, whereby the side chain portion, It can have a double bond in a portion other than the main chain of the copolymer.

  The repeating unit (a) derived from the olefin monomer, the repeating unit (b) derived from the cyclic olefin monomer (b), and the side included in the cyclic olefin (co) polymer (B) according to the present embodiment Derived from the monomer (c) having a crosslinkable double bond in the side chain portion when the total number of moles with the repeating unit (c) derived from the monomer (c) having a crosslinkable double bond in the chain portion is 100 mol% The proportion of the repeating unit (c) is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 45 mol%, and still more preferably 5 mol% to 40 mol%.

In particular, when the ratio of the repeating unit (c) derived from the monomer (c) having a crosslinkable double bond in the side chain portion is within the above range, the obtained cured product is more stable over time in dielectric properties. Excellent and heat resistance. Furthermore, a cured product having excellent mechanical properties, dielectric properties, and transparency can be obtained. In other words, a cured product having an excellent balance of physical properties can be obtained.
By controlling the proportion of the structural unit (c) derived from the monomer (c) having a crosslinkable double bond in the side chain portion to be not more than the above upper limit, the moldability and solubility of the cyclic olefin (co) polymer (B) It is possible to further improve the temporal stability of the dielectric properties of the cured product while improving the resistance. Moreover, the heat resistance of a hardened | cured material and a mechanical characteristic are improved further by making the ratio of the structural unit (c) derived from the monomer (c) which has a crosslinkable double bond in a side chain part more than the said lower limit. be able to.

The number of double bonds per repeating unit (c) can be appropriately set depending on the use, but as a monomer (c) having a crosslinkable double bond in the side chain portion from which it is derived, a viewpoint of reaction control and the like To 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and at least one diene compound selected from the group consisting of dicyclopentadiene are preferable, and 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and dicyclopentadiene are more preferable, and 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is more preferred, and 5-vinyl-2-norbornene is particularly preferred.

  The cyclic olefin (co) polymer (B) according to the present embodiment can control the comonomer content and the glass transition temperature (Tg) according to the charge ratio of the monomers according to the intended use. Tg of the cyclic olefin (co) polymer (B) according to this embodiment is usually 50 ° C. or higher and 300 ° C. or lower, preferably 60 ° C. or higher and 250 ° C. or lower, particularly preferably 70 ° C. or higher and 200 ° C. or lower. It is. The moldability of cyclic olefin (co) polymer (B) can be further improved as Tg is below the said upper limit. Moreover, the heat resistance and mechanical characteristics of the hardened | cured material which a Tg is more than the said lower limit improve.

From the viewpoint of improving the impregnation property of the polyphenylene ether resin composition into the sheet-like fiber base material or the like when producing the prepreg, the cyclic olefin (co) polymer (B) according to the present embodiment is in decalin at 135 ° C. The intrinsic viscosity [η] measured in (1) is, for example, 0.01 to 1.0 dl / g, preferably 0.05 to 0.7 dl / g, more preferably 0.10 to 0.5 dl / g. It is.
The intrinsic viscosity [η] of the cyclic olefin (co) polymer (B) can be controlled by polymerization conditions such as a polymerization catalyst, a cocatalyst, the amount of H ₂ added, and a polymerization temperature.

  Here, examples of the ring-opening polymer of the cyclic olefin include, for example, a ring-opening polymer of a norbornene-based monomer and a ring-opening weight of the norbornene-based monomer and other monomers capable of ring-opening copolymerization therewith. And hydrides thereof, and the like.

Examples of the norbornene-based monomer include bicyclo [2.2.1] -2-heptene (common name: norbornene) and its derivatives (having a substituent in the ring), tricyclo [4.3.01, 6 .12,5] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name methano) Tetrahydrofluorene: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. In addition, a substituent can have 1 piece or 2 or more pieces. As a derivative having a substituent in such a ring, for example, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers are used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst.
As the ring-opening polymerization catalyst, for example, a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; a metal halide such as titanium, zirconium, tungsten or molybdenum or an acetylacetone compound A catalyst comprising an organoaluminum compound; and the like can be used.
Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  A hydride of a ring-opening polymer of a norbornene monomer or a hydride of a ring-opening polymer of a norbornene monomer and another monomer capable of ring-opening copolymerization with the ring-opening polymer is usually the above-mentioned ring-opening polymer. It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymer solution and hydrogenating the carbon-carbon unsaturated bond.

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

[Compatibilizer (C)]
The polyphenylene ether resin composition according to the present embodiment improves the compatibility between the polyphenylene ether (A) and the cyclic olefin (co) polymer (B) and balances performance such as dielectric properties, heat resistance, and thermal stability. From the viewpoint of obtaining a more excellent cured product, it is preferable to further contain a compatibilizer (C) that compatibilizes the polyphenylene ether (A) and the cyclic olefin (co) polymer (B).
Examples of the compatibilizing agent (C) include a modified polyolefin, a modified elastomer, and a compound having a polar group and an unsaturated carbon bond that can contribute to the polymerization reaction in the molecule.

Examples of the modified polyolefin include polyolefin obtained by grafting or graft polymerization of a monomer having a polar group, and a copolymer of an olefin and a monomer having a polar group.
Of these, polyolefins grafted with monomers having polar groups are preferred. Here, “grafting” refers to introducing a compound having a polar group into a backbone polymer as a main chain. “Graft-polymerized” refers to introducing a branched polymer made of a polymer different from the main chain into the main polymer as the main chain.

  Examples of polar groups include amino groups, hydroxyl groups, carboxyl groups, epoxy groups, nitrile groups, nitro groups, aldehyde groups, amide groups, ester groups, acid anhydrides, and the like. These are used individually or in combination of 2 or more types. Among these, at least one selected from a carboxyl group and an acid anhydride is preferable from the viewpoint of further improving the mechanical strength of the obtained cured product.

  As monomers having such polar groups, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinylpyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Propyl methacrylate, 2-hydroxypropyl acrylate, oxazoline, etc.The said compound can be used individually or in combination of 2 or more types. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable.

  Polyolefins such as polyethylene, polypropylene, ethylene / α-olefin copolymer, propylene / 1-butene copolymer, propylene / α-olefin copolymer, poly-4-methylpentene, polybutene, etc. Or oligomers, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, chlorosulfinated polyethylene, ethylene vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, chlorine Polyethylene, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like. These can be used alone or in combination of two or more.

  Examples of the polyolefin grafted with a monomer having a polar group include a propylene / 1-butene copolymer grafted with a monomer having a polar group.

Examples of the modified elastomer include an elastomer obtained by grafting or graft polymerization of a monomer having a polar group.
Examples of polar groups include amino groups, hydroxyl groups, carboxyl groups, epoxy groups, nitrile groups, nitro groups, aldehyde groups, amide groups, ester groups, acid anhydrides, and the like. These are used individually or in combination of 2 or more types. Among these, at least one selected from a carboxyl group and an acid anhydride is preferable from the viewpoint of further improving the mechanical strength of the obtained cured product.

  As monomers having such polar groups, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinylpyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Propyl methacrylate, 2-hydroxypropyl acrylate, oxazoline, etc.The said compound can be used individually or in combination of 2 or more types. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable.

  Examples of elastomers include styrene / conjugated diene block copolymer resins (such as butadiene and isoprene as conjugated dienes), hydrogenated styrene / conjugated diene block copolymer resins (such as butadiene and isoprene as conjugated dienes), Styrene, conjugated diene, styrene triblock copolymer resin (butadiene, isoprene, etc. as conjugated diene), hydrogenated products of styrene, conjugated diene, styrene triblock copolymer resin (butadiene, isoprene, etc. as conjugated diene), etc. Styrene elastomers: natural rubber, polyisoprene rubber, polybutadiene rubber, nitrile rubber (acrylonitrile-butadiene copolymer), chloroprene rubber, butyl rubber, acrylic rubber, polyurethane elastomer, silicone rubber, epichlorohydride Ngomu, synthetic rubbers such as nitrile-isoprene rubber; polyester elastomers, urethane elastomers, and the like. These can be used alone or in combination of two or more.

  Examples of the elastomer grafted with such a monomer having a polar group include a maleic acid-modified elastomer such as a hydrogenated styrene / butadiene block copolymer grafted with maleic anhydride.

  Furthermore, the compatibilizing agent (C) is not limited to a high molecular compound typified by the above-described modified polyolefin or modified elastomer, and a low molecular compound having no repeating unit can be used.

  As such a low molecular weight compound, a compound having a polar group and an unsaturated carbon bond that can contribute to the polymerization reaction in the molecule is preferable. Examples of the polar group shown here include amino group, hydroxyl group, carboxyl group, epoxy group, nitrile group, nitro group, aldehyde group, amide group, ester group, glycidyl group and the like. Among these, an epoxy group and a glycidyl group are preferable from the viewpoint of further improving the mechanical strength of the obtained cured product.

  As a compound having a polar group and an unsaturated carbon bond that can contribute to the polymerization reaction in the molecule, acrylic acid, methacrylic acid, or derivatives thereof are preferably used from the viewpoint of availability.

Examples of acrylic acid derivatives include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, acrylamide, N-cyclopropylacrylamide, N, N-dimethylacrylamide, N-hydroxymethylacrylamide, N-isopropylacrylamide. And acrylonitrile.
Examples of methacrylic acid derivatives include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, methacrylamide, N-cyclopropylmethacrylamide, N, N-dimethylmethacrylamide, N-hydroxymethylmethacrylate. Examples include amide, N-isopropylmethacrylamide, methacrylonitrile and the like.
Among these, glycidyl methacrylate is preferable from the viewpoint of further improving the mechanical strength of the obtained cured product.

Although the example of the compound which can be used as a compatibilizing agent (C) was enumerated above, these can also be used independently and can also be used in combination of multiple types.
The content of the compatibilizer (C) is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 1 part, when the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by weight. Part to 5 parts by weight, particularly preferably 2 parts to 5 parts by weight.

[varnish]
The polyphenylene ether resin composition according to this embodiment can be made into a varnish by mixing with a solvent. The solvent for adjusting the varnish is not particularly limited as long as it does not impair the solubility or affinity for the polyphenylene ether (A) and the cyclic olefin (co) polymer (B). 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 produced by any method, but usually includes a step of mixing the polyphenylene ether resin composition and the solvent. About mixing of each component, there is no restriction | limiting in the order, It can implement by what kind of methods, such as lump or division. There is no restriction | limiting as an apparatus which prepares a varnish, You may implement by what kind of apparatus of a batch type or a continuous type which can be stirred and mixed. The temperature for preparing the varnish can be arbitrarily selected in the range from room temperature to the boiling point of the solvent.
In addition, you may prepare a varnish by using the reaction solution at the time of obtaining a cyclic olefin (co) polymer (B) as a solvent as it is, and dissolving polyphenylene ether (A) there. Moreover, after refine | purifying a cyclic olefin (co) polymer (B), you may prepare a varnish by adding a polyphenylene ether (A) and a solvent separately.

[Hardened product]
The cured product according to the present embodiment is a cured product of the polyphenylene ether resin composition according to the present embodiment, and is obtained by curing the polyphenylene ether resin composition. Although there is no restriction | limiting in particular as a hardening method of a polyphenylene ether resin composition, The method etc. which harden | cure while shape | molding in arbitrary forms using a radical polymerization initiator, an electron beam, and other radiation, etc. are mentioned. .

  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 polyphenylene ether (A) and the cyclic olefin (co) polymer (B) according to this embodiment, and heated and cured. Although the blending ratio of the radical polymerization initiator is not particularly limited, it is usually 0.02 to 20 parts by mass per 100 parts by mass in total of the polyphenylene ether (A) and the cyclic olefin (co) polymer (B), preferably It is 0.05-10 mass parts, More preferably, it is 0.5-10 mass parts. When the blending ratio of the radical polymerization initiator is not more than the above upper limit value, the dielectric properties of the cured product are improved, and when it is not less than the above lower limit value, the heat resistance and mechanical properties of the cured product can be improved.

  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.

  Among the radical polymerization initiators, specific examples of the photo radical polymerization initiator include benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, benzophenone, methylbenzoyl formate, isopropylthioxanthone, 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 polyphenylene ether resin composition according to this embodiment is cured with a radical polymerization initiator, the curing temperature is usually 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 120 to 250 ° C, Curing may be carried out by changing stepwise. When it is at least the lower limit, curing can be sufficiently advanced. Moreover, coloring of the hardened | cured material obtained as it is below the said upper limit can be suppressed, or a process can be simplified.

  The method of curing using an electron beam or other radiation has an advantage that there is no limitation on temperature and fluidity during molding, and examples of the radiation include γ rays, UV, etc. in addition to electron beams. .

  In either case of a method using a radical polymerization initiator or a method of curing using radiation, curing can be carried out in combination with a crosslinking aid (D).

Although there is no restriction | limiting in particular as a crosslinking adjuvant (D), For example, oximes, such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; Ethylene dimethacrylate, polyethyleneglycol dimethacrylate, trimethylol propane tri Acrylates or methacrylates such as methacrylate and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene and vinylpyridine; hexamethylene diallyl nadiimide, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate And allyl compounds such as N, N′-m-phenylenebismaleimide and N, N ′-(4,4′-methylenediphenylene) dimaleimide; vinyl norbornene; And cyclic non-conjugated dienes such as ethylidene norbornene and dicyclopentadiene; polybutadiene and the like. These crosslinking aids (D) may be used alone or in combination.
Among these, at least one selected from divinylbenzene and polybutadiene is 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.

  In the case where the polyphenylene ether resin composition according to the present embodiment contains a crosslinking aid (D), the polyphenylene ether is obtained from the viewpoint of further improving the heat resistance while satisfying good thermal stability and dielectric properties. When the content of the polyphenylene ether (A) in the resin composition is 100 parts by mass, the content of the cyclic olefin (co) polymer (B) is 2 parts by mass or more and less than 20 parts by mass, The content of D) is preferably 5 parts by mass or more and 50 parts by mass or less.

  The polyphenylene ether resin composition or cured product 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, and a dye as necessary. , Pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, thermoplastic resins other than polyphenylene ether (A) and cyclic olefin (co) polymer (B), thermosetting resins, etc. Can be blended to such an extent that does not spoil, and 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, and pentaerythritol tristearate . 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.

As the flame retardant, for example, an antimony flame retardant, a halogen flame retardant, or a phosphorus flame retardant can be used.
Examples of the antimony flame retardant include antimony oxide, antimony pentoxide, antimony tetroxide, and sodium antimonate.
As the halogen flame retardant, various chlorine and bromine flame retardants can be used. However, the flame retardant effect, the heat resistance during molding, the dispersibility in the resin, the influence on the physical properties of the resin, etc. From the surface, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide , Decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [for example, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobiphenyl Phenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) and the like], tetrabromobisphenol S, and derivatives thereof [for example, Tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc.], tetrabromophthalic anhydride, and derivatives thereof [for example, tetrabromophthalimide, ethylenebistetrabromophthalimide Etc.], ethylenebis (5,6-dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, hexachlorocyclopentadiene deal・ Alder reaction adduct, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bistribromophenyl ether, ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy Brominated flame retardants such as resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine; chlorinated paraffins such as chlorinated paraffin It is preferable to use a flame retardant.

  Examples of the phosphorus flame retardant include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, and tris (bromo). Halogen-containing phosphoric acid such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate Ester flame retardants; Aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyl di Phenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tri (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tri (trimethylphenyl) phosphate, tri ( Non-halogen phosphate ester flame retardants such as aromatic phosphates such as t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, and octyl diphenyl phosphate.

  Organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite Talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, Polyamide fiber etc. are mentioned.

  In order to mix the polyphenylene ether resin composition or cured product and various additives according to the present embodiment, a method of melt-blending the polyphenylene ether resin composition and various additives with an extruder or the like, or the polyphenylene ether resin composition and various additives Adopting a solution blend method in which the additive is dissolved and dispersed in an appropriate solvent, for example, a saturated hydrocarbon such as heptane, hexane, decane or cyclohexane; an aromatic hydrocarbon such as toluene, benzene or xylene. Can do.

  The curing reaction can also be performed in a molten state of a mixture of the polyphenylene ether resin composition according to the present embodiment and a compound that undergoes curing such as the above-described radical polymerization initiator. The mixture can be dissolved or dispersed in a solvent, or the solvent is volatilized from the solution dissolved in the solvent and formed into an arbitrary shape such as a film or a coating, followed by further curing reaction. You can also.

  When the reaction is performed in a molten state, the mixture of raw materials is melt-kneaded and reacted using a kneading apparatus such as a mixing roll, a Banbury mixer, an extruder, a kneader, or a continuous mixer. Moreover, after shaping | molding by arbitrary methods, hardening reaction can also be advanced.

  As the solvent used when the reaction is performed in a solution state, the same solvent as the solvent used in the solution blending method can be used.

  When the curing reaction is performed using an electron beam, other radiation, or UV, the reaction can be performed after shaping by any method.

Since the cured product according to the present embodiment is excellent in solvent resistance, heat resistance, and mechanical strength, a molded body containing the cured product is a coating material for organic EL, a base film substrate for solar cells in the aerospace field, Pre-pregs and laminates used to form solar cell and thermal control system coating materials, semiconductor elements, light-emitting diodes, electronic elements such as various memories, hybrid ICs, MCMs, printed wiring boards, and printed wiring board insulation layers It can be used in applications such as overcoat materials such as display parts or interlayer insulating materials, substrates for liquid crystal displays and solar cells.
In particular, because it is excellent not only in dielectric properties, heat resistance and thermal stability, but also in mechanical properties, etc., a high-frequency printed wiring board, a film or sheet used to form an insulating layer of the high-frequency printed wiring board, a prepreg, It can be suitably used for a laminate or the like.

[Dry film, film or sheet]
The polyphenylene ether resin composition according to this embodiment can be formed into a dry film, a film or a sheet and used for various applications. As a method of forming a dry film, a film or a sheet using the polyphenylene ether resin composition according to this embodiment, various known methods can be applied. For example, there may be mentioned a method in which the varnish described above is applied onto a supporting substrate such as a thermoplastic resin film, dried, and then heat-treated to cure the polyphenylene ether resin composition. Although the coating method to the support base material of a varnish is not specifically limited, For example, the application | coating using a spin coater, the application | coating using a spray coater, the application | coating using a bar coater etc. can be mentioned.
Moreover, the method of melt-molding the polyphenylene ether resin composition of this embodiment and obtaining a dry film, a film, or a sheet | seat can also be mentioned.

[Laminate]
The film of this embodiment can be used for various applications as a laminate by laminating on a substrate. Various known methods can be applied to the method of forming the laminate of the present embodiment.
For example, a laminate can be produced by laminating the dry film, film or sheet produced by the above-described method on the conductor layer, and heat-curing with a press or the like, if necessary.
Moreover, a laminated body can also be produced by laminating an electrical insulating layer containing a cured product according to this embodiment on a substrate having a conductor layer on the surface.

[Prepreg]
Moreover, the prepreg according to the present embodiment is formed by combining the polyphenylene ether resin composition of 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. For example, the batch-type drying is performed in air or nitrogen using a blow dryer, or the heating furnace is used 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, but usually 10 to 90 mass in the prepreg or laminate. %, Preferably 20 to 80% by mass, more preferably 30 to 70% by mass. Within this range, the dielectric properties and mechanical strength of the resulting laminate 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, Usually, it is 0.001-10 mm, Preferably it is 0.005-1 mm, More preferably, it is 0.01-0. 5 mm. If it exists in this range, the shapeability at the time of lamination | stacking and characteristics, such as the mechanical strength of a laminated body obtained by hardening, and toughness, will fully be exhibited and it is suitable.

The dry film, film, or prepreg according to this 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.

[Printed wiring board]
As described above, the polyphenylene ether resin composition according to the present embodiment is excellent in the performance balance of dielectric properties, heat resistance, and thermal stability, and therefore can be suitably used for a printed wiring board.
A generally known method can be adopted as a method for producing a printed wiring board, and is not particularly limited. Form. Next, a conductor layer is laminated on the obtained electrical 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 for forming the conductor layer, in addition to the method of heat-sealing the metal to a cured product using a foil or the like, lamination is performed using an adhesive, or sputtering, vapor deposition, plating, or the like. It can be manufactured by a forming method. As an aspect of a laminated body, either a single-sided board or a double-sided board may be sufficient.

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 composition and intrinsic viscosity [η] of the cyclic olefin (co) polymer (B) used in the synthesis examples, examples and comparative examples were measured by the following methods.

Composition: ¹ H-NMR measurement was performed, and the cyclic non-conjugated diene content was calculated from the intensity of the hydrogen-derived peak directly bonded to the double bond carbon and the other hydrogen peaks.

  Intrinsic viscosity [η]; measured in decalin at 135 ° C.

  The following raw materials were used for the experiment.

Transition metal compound (1):
The compound was synthesized by the method described in JP-A-2004-331965.

Transition metal compound (2): CpTiCl ₂ (N = C ^t Bu ₂ )
J. et al. Am. Chem. Soc. 2000, 122, 5499-5509. Was synthesized based on the description.

(Polyphenylene ether (A))
Polyphenylene ether (A-1): Modified polyphenylene ether synthesized according to Synthesis Example 1 below Polyphenylene ether (A-2): Modified polyphenylene ether in which terminal hydroxyl group of polyphenylene ether of formula (7) is modified with methacrylic group (SABIC Innovative) SA9000 made by Plastics)

(Cyclic olefin (co) polymer (B))
Cyclic olefin (co) polymer (B-1): Cyclic olefin copolymer synthesized according to Synthesis Example 2 below ([η] = 0.40 dl / g)
Cyclic olefin (co) polymer (B-2): Cyclic olefin copolymer synthesized according to Synthesis Example 3 below ([η] = 0.17 dl / g)
Cyclic olefin (co) polymer (B-3): A copolymer composed of ethylene and bicyclo [2.2.1] -2-heptene (product name: TOPAS 6013S-04, manufactured by Polyplastics, [η] = 0.58 dl / g)
Cyclic olefin (co) polymer (B-4): Ring-opening polymer of cyclic olefin (Product name: ZEONEX 480, manufactured by Nippon Zeon Co., Ltd., [η] = 0.42 dl / g)

(Compatibilizer (C))
Compatibilizer (C-1): synthesized according to Synthesis Example 4 below.

(Other)
MMAO (manufactured by Tosoh Finechem)
MAO (Nippon Alkyl Aluminum Co., Ltd.)
5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (Mitsui Chemicals, Inc.)
Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D)
Divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polybutadiene (Nippon Soda Co., Ltd., B-3000)

[Synthesis Example 1: Synthesis of polyphenylene ether (A-1)]
It was synthesized according to the synthesis of modified polyphenylene ether 1 (modified PPE1) in International Publication No. 2014/203511. Specifically, it is as follows.
To a glass reactor charged with 200 g of toluene, 100 g of a polyphenylene ether oligomer (SA90 manufactured by SABIC), 15 g of chloromethylstyrene, and 0.6 g of tetrabutylammonium bromide were added and heated to 75 ° C. with stirring to dissolve. Next, 20 g of a 50 wt% aqueous sodium hydroxide solution was added dropwise and stirred at 75 ° C. for 4 hours. Thereafter, the mixture was neutralized with hydrochloric acid, and methanol was added to precipitate the product. The precipitated product was washed with a solution in which methanol and water were mixed at a weight ratio of 80:20, and then dried at 80 ° C. under reduced pressure for 10 hours to obtain terminal vinyl-modified polyphenylene ether (number average molecular weight Mn = 2300). It was.

[Synthesis Example 2: Synthesis of cyclic olefin (co) polymer (B-1)]
A SUS autoclave with an internal volume of 4 L that was sufficiently purged with nitrogen was charged with 1670 ml of xylene, 212 ml of 5-vinyl-2-norbornene (VNB), tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (TD) 120 ml, MMAO (manufactured by Tosoh Finechem Co.) in toluene, 4 mmol in terms of Al, and hydrogen 1984 ml are added, until ethylene reaches a total pressure of 0.6 MPa. Introduced. 0.04 mmol of the transition metal compound (1) was dissolved in 10 ml of toluene and added to initiate polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 25 ° C. for 60 minutes, and then the polymerization was stopped by injecting 5 ml of methanol. After completion of the polymerization, the reaction product was put into a mixed solvent of 15 L of acetone and 5 L of methanol to which 20 ml of concentrated hydrochloric acid had been added to precipitate the whole amount of the polymer. After stirring, the reaction product was filtered through a filter paper. The entire polymer obtained by repeating this operation until the reaction product disappeared was dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / TD / VNB copolymer. The intrinsic viscosity [η] was 0.40 (dL / g), the composition ratio of the VNB-derived structure in the polymer determined by NMR was 25.7 mol%, and the composition ratio of the TD-derived structure was 10.6 mol%.

[Synthesis Example 3: Synthesis of cyclic olefin (co) polymer (B-2)]
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-hexene 28.2 mL, methylaluminoxane (MAO) 10 mmol in terms of aluminum atom was added. 0.010 mmol of transition metal compound (2) dissolved in toluene was further 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 poured into a mixed solvent of acetone / methanol (500 ml each) to which 0.5 mL of concentrated hydrochloric acid was added to precipitate the entire amount of the polymer, and after stirring, the solution was filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, a TD / 1-hexene copolymer was obtained. The monomer composition in the polymer determined by NMR analysis was TD 35 mol%, 1-hexene 65 mol%, and the glass transition temperature measured by DSC was 188 ° C.
Here, the NMR analysis method followed the method described in Macromolecules 2016, 49, 59-70.

[Synthesis Example 4: Synthesis of Maleic Anhydride Modified Polystyrene / Polybutadiene / Polystyrene Triblock Copolymer (Compatibilizer (C-1))]
In a 1.0 L glass autoclave equipped with a stirring blade, a hydrogenated product of polystyrene / polybutadiene / polystyrene triblock copolymer (manufactured by Shell Chemical Co., Kraton G1652, number average molecular weight: 8.5 × 10 ⁴ , styrene) Content: 30% by mass) 105 g and dehydrated toluene 340 ml were added and heated to 165 ° C. to dissolve. Subsequently, a solution in which 3.46 g of maleic anhydride was dissolved in 40 ml of dehydrated toluene and a solution in which 0.31 g of di-t-butyl peroxide was dissolved in 40 ml of dehydrated toluene were prepared. It was dripped sequentially. After completion of dropping, the reaction was carried out at 165 ° C. for 2 hours.
It was 3.5 mass% when the maleic anhydride graft amount of the obtained modified copolymer was measured by oxygen analysis.

[Examples 1 to 13 and Comparative Examples 1 to 6]
First, each component was added to toluene at the blending ratios shown in Tables 1 and 2 (the numerical values in the table indicate parts by mass) and mixed to form a varnish-like polyphenylene ether resin composition (resin varnish). Prepared.

  The obtained resin varnish was applied on 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. Subsequently, it heated up at 200 degreeC and heated for 2 hours, and obtained the film which consists of a crosslinked body, respectively. Subsequently, the obtained film was peeled off from the PET film, and the following dielectric loss tangent, heat resistance and thermal stability were evaluated. The obtained results are shown in Tables 1 and 2, respectively.

(1) 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. A test piece cut into a length of 50 mm and a width of 5 mm was used for the measurement. The heat resistance of the polyphenylene ether resin composition was evaluated according to the following criteria.
◎: 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) Dielectric loss tangent The dielectric loss tangent of the film at 12 GHz was measured by a cylindrical cavity resonator method. Specifically, the dielectric loss tangent of the film 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).

(3) Thermal stability The obtained film was put into an oven at a temperature of 200 ° C. and taken out after 100 hours. The thermal stability was evaluated from the state of the film taken out.
The thermal stability of the polyphenylene ether resin composition was evaluated according to the following criteria.
○: No abnormality ×: The film has cracks

[Example 14 and Comparative Example 7]
(Preparation of resin varnish)
First, polyphenylene ether (A), cyclic olefin (co) polymer (B), compatibilizer (C), radical polymerization initiator, and crosslinking aid (D) are mixed in the proportions shown in Table 3 (in the table Numerical values indicate parts by mass), and added to toluene and mixed to prepare a varnish-like polyphenylene ether resin composition (resin varnish).

(Preparation of prepreg)
Next, the obtained polyphenylene ether resin composition varnish was impregnated into a glass cloth (manufactured by Arisawa Manufacturing Co., Ltd., 1031NT S640) and dried at 120 ° C. for 10 minutes in a blower dryer, whereby a prepreg having a thickness of 0.1 mm was obtained. Produced.

(Production of laminate)
Eight prepregs cut into 150 mm squares were stacked, and heated for 2 hours at a pressure of 3.5 MPa and 200 ° C. with a vacuum press machine to prepare laminates.
The following dielectric loss tangents were evaluated for the obtained laminates. The obtained results are shown in Table 3, respectively.

(Preparation of copper-clad laminate)
By stacking 8 sheets of prepreg cut into 150 mm square, and further stacking copper foil (F1-WS, manufactured by Furukawa Electric Co., Ltd.) on both sides of the prepreg, heating it at a pressure of 3.5 MPa and 200 ° C. for 2 hours with a vacuum press Copper-clad laminates to which copper foils were bonded were produced.
The obtained copper-clad laminate was evaluated for the following solder heat resistance and peel strength. The obtained results are shown in Table 3, respectively.

(1) Dielectric loss tangent 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).

(2) Solder heat resistance The state after immersing the copper clad laminate in a solder bath at 288 ° C. for 20 seconds was observed.
○: Both deformation and blister did not occur. ×: At least one of deformation and blister occurred.

(3) Peel strength Based on JIS C6481, the copper foil was peeled from the copper clad laminate, and the peel strength at that time was measured.
The case where the strength was 0.4 kN / m or more was rated as ◯, and the case where the strength was less than 0.4 kN / m was rated as x.

As can be seen from Table 1, it was found that the films of Examples 1 to 13 were excellent in heat resistance and thermal stability while satisfying dielectric properties in a high frequency region suitable for a printed wiring board. Moreover, it turned out that the laminated body of Example 14 and a copper clad laminated board are excellent also in heat resistance and adhesiveness, satisfying the dielectric characteristic in the high frequency area | region suitable for a printed wiring board.
In contrast, Comparative Examples 1, 2, and 7 that do not contain a cyclic olefin (co) polymer (B) have a high dielectric loss tangent and poor dielectric properties, and a comparative example with a large proportion of the cyclic olefin (co) polymer (B). 3 to 6 had low dielectric loss tangent and excellent dielectric properties, but were inferior in thermal stability.

Claims (21)

A polyphenylene ether resin composition comprising a polyphenylene ether (A) and a cyclic olefin (co) polymer (B),
The ratio of the content of the polyphenylene ether (A) to the content of the cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition ((A) / (B)) is more than 5 and 50 or less. Polyphenylene ether resin composition. In the polyphenylene ether resin composition according to claim 1,
The cyclic olefin (co) polymer (B) is
A repeating unit (a) derived from at least one 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) A polyphenylene ether resin composition comprising a repeating unit (b) derived from the same.

(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 polyphenylene ether resin composition according to claim 2,
The cyclic olefin-derived repeating unit (b) in the cyclic olefin (co) polymer (B) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5. . A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from 1 ^7,10 ] -3-dodecene. In the polyphenylene ether resin composition according to claim 2 or 3,
The cyclic olefin (co) polymer (B) is a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating represented by the following general formula (VII) A polyphenylene ether resin composition further comprising a repeating unit (c) derived from at least one non-conjugated diene-based olefin selected from the group consisting of units.

(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 polyphenylene ether resin composition according to claim 4,
The polyphenylene ether in which the repeating unit (c) derived from the non-conjugated diene-based olefin in the cyclic olefin (co) polymer (B) includes a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (VII) Resin composition. In the polyphenylene ether resin composition according to claim 4 or 5,
The repeating unit (c) derived from the non-conjugated diene olefin in the cyclic olefin (co) polymer (B) is 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo [4.4.0. .1 ^2,5 . A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from 1 ^7,10 ] -3-dodecene. In the polyphenylene ether resin composition according to any one of claims 1 to 6,
A polyphenylene ether resin composition having an intrinsic viscosity [η] in decalin of 135 ° C. of 0.01 to 1.0 dl / g of the cyclic olefin (co) polymer (B). In the polyphenylene ether resin composition according to any one of claims 1 to 7,
A polyphenylene ether resin composition comprising a modified polyphenylene ether in which the polyphenylene ether (A) is modified with a substituent having a carbon-carbon unsaturated bond. In the polyphenylene ether resin composition according to any one of claims 1 to 8,
A polyphenylene ether resin composition further comprising a crosslinking aid (D). In the polyphenylene ether resin composition according to claim 9,
When the content of the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by mass,
The content of the cyclic olefin (co) polymer (B) is 2 parts by mass or more and less than 20 parts by mass,
The polyphenylene ether resin composition whose content of the said crosslinking adjuvant (D) is 5 to 50 mass parts. In the polyphenylene ether resin composition according to any one of claims 1 to 10,
A polyphenylene ether resin composition wherein the polyphenylene ether (A) has a number average molecular weight of 500 or more and 7,000 or less. In the polyphenylene ether resin composition according to any one of claims 1 to 11,
A polyphenylene ether resin composition further comprising a compatibilizing agent (C) for compatibilizing the polyphenylene ether (A) and the cyclic olefin (co) polymer (B). In the polyphenylene ether resin composition according to claim 12,
A polyphenylene ether resin composition comprising the compatibilizer (C) containing at least one selected from a modified polyolefin and a modified elastomer. In the polyphenylene ether resin composition according to claim 12 or 13,
A polyphenylene ether resin composition in which the content of the compatibilizer (C) is 0.1 parts by mass or more and 10 parts by mass or less when the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by mass. object.   Hardened | cured material formed by hardening | curing the polyphenylene ether resin composition as described in any one of Claims 1 thru | or 14.   The dry film which consists of a polyphenylene ether resin composition as described in any one of Claims 1 thru | or 14.   A film obtained by curing the dry film according to claim 16.   A prepreg comprising the polyphenylene ether resin composition according to any one of claims 1 to 14 and a sheet-like fiber base material.   A metal-clad laminate obtained by laminating at least one selected from the dry film according to claim 16, the film according to claim 17, and the prepreg according to claim 18 and a metal foil.   An electrical insulating layer formed of at least one selected from the dry film according to claim 16, the film according to claim 17, and the prepreg according to claim 18, and a conductor provided on the electrical insulating layer Printed circuit board comprising a layer.   The electronic device provided with the printed wiring board of Claim 20.