JP6803181B2 - Polyphenylene ether resin composition, cured product, dry film, film, prepreg, metal-clad laminate, printed wiring board and electronic equipment - Google Patents

Description

The present invention relates to polyphenylene ether resin compositions, cured products, dry films, films, prepregs, metal-clad laminates, printed wiring boards and electronic devices.

In recent years, in addition to the increase in wireless communication devices and the like that use a high frequency band, the frequency band in a high band is inevitably often used due to the increase in communication speed. Along with this, a printed wiring board material having a small dielectric loss tangent is required in order to reduce transmission loss at high frequencies to the utmost 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) describes (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 cross-linking agent containing (B-1) divinylbenzene and (B-2) polybutadiene contains 50 to 100% by mass of the component (A) and the component (B). The content ratio is the mass ratio, and 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 the mass ratio. A polyphenylene ether resin composition is described, wherein the component (B-1): component (B-2) = 1: 100 to 1.5: 1.

International Publication No. 2014/203511

In recent years, the required characteristics of an insulating layer used for a printed wiring board have been further increased, and an insulating resin material having heat resistance, dielectric characteristics and thermal stability is required.
According to the studies by the present inventors, there is room for improvement in the conventional polyphenylene ether resin composition from the viewpoint of improving the dielectric properties, heat resistance, and thermal stability of the obtained cured product in a well-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 having excellent heat resistance and thermal stability while satisfying dielectric properties in a high frequency region suitable for a printed wiring board. It provides a resin composition.

As a result of diligent studies to solve the above problems, the present inventors have obtained a high frequency by mixing the polyphenylene ether and the cyclic olefin (co) polymer in a specific ratio while satisfying heat resistance and thermal stability. We have found that the dielectric properties in the region are improved, and completed the present invention.

The present invention is as shown below.

（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、
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。
［９］
上記［８］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。
［１０］
上記［１］乃至［９］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。
［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）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。
［１２］
上記［１１］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。
［１３］
上記［１１］または［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）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。
［１４］
上記［１］乃至［１３］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。
［１５］
上記［１］乃至［１３］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。
［１６］
上記［１５］に記載のドライフィルムを硬化してなるフィルム。
［１７］
上記［１］乃至［１３］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。
［１８］
上記［１５］に記載のドライフィルム、上記［１６］に記載のフィルム、および上記［１７］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。
［１９］
上記［１５］に記載のドライフィルム、上記［１６］に記載のフィルム、および上記［１７］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。
［２０］
上記［１９］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 containing a polyphenylene ether (A) and a cyclic olefin (co) polymer (B).
The ratio ((A) / (B)) of the content (mass) of the polyphenylene ether (A) to the content of the cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition exceeds 5 50. It der below,
A polyphenylene ether resin composition, wherein the polyphenylene ether (A) contains a modified polyphenylene ether modified by a substituent having a carbon-carbon unsaturated bond .
[2]
In the polyphenylene ether resin composition according to the above [1],
The cyclic olefin (co) polymer (B)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
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 containing the derived repeating unit (b).

(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.)

(In the above 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 identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.)

(In the above 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 or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. There, 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 directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, 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 or different from each other, and represent 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. .. 1 ^{7, 10} ] A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from -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 unit represented by the following general formula (VII). A polyphenylene ether resin composition further containing a repeating unit (c) derived from at least one non-conjugated diene olefin selected from the group consisting of units.

(In the above 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 has 1 to 20 carbon atoms. It is a straight or branched hydrocarbon group and may contain double and / or triple bonds.)

(In the above 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 identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ~ 20 aromatic hydrocarbon groups, R ¹⁰² and R ¹⁰³ may be the same or different from each other, are hydrogen atoms or alkyl groups with 1 to 10 carbon atoms, and R ⁷⁵ and R ⁷⁶ are bonded to each other. It may form a monocyclic ring or a polycyclic ring.)

(In the above 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 identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ~ 20 aromatic hydrocarbon groups, R ¹⁰⁴ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. May form a monocyclic ring or a polycyclic ring.)
[5]
In the polyphenylene ether resin composition according to the above [4],
The repeating unit (c) derived from the non-conjugated diene olefin in the cyclic olefin (co) polymer (B) contains 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 . 1 ^{7, 10} ] A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from -3-dodecene.
[7]
In the polyphenylene ether resin composition according to any one of the above [1] to [6],
A polyphenylene ether resin composition of the cyclic olefin (co) polymer (B) having an intrinsic viscosity [η] in decalin at 135 ° C. of 0.01 dl / g or more and 1.0 dl / g or less.
[ 8 ]
In the polyphenylene ether resin composition according to any one of the above [1] to [ 7 ],
A polyphenylene ether resin composition further containing a cross-linking aid (D).
[ 9 ]
In the polyphenylene ether resin composition according to the above [ 8] ,
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.
A polyphenylene ether resin composition having a content of the cross-linking aid (D) of 5 parts by mass or more and 50 parts by mass or less.
[ 10 ]
In the polyphenylene ether resin composition according to any one of the above [1] to [ 9 ],
A polyphenylene ether resin composition having a number average molecular weight of the polyphenylene ether (A) of 500 or more and 7,000 or less.
[ 11 ]
In the polyphenylene ether resin composition according to any one of the above [1] to [ 10 ],
A polyphenylene ether resin composition further containing a compatibilizer (C) for compatibilizing the polyphenylene ether (A) and the cyclic olefin (co) polymer (B).
[ 12 ]
In the polyphenylene ether resin composition according to the above [ 11 ],
A polyphenylene ether resin composition containing at least one compatibilizer (C) selected from modified polyolefins and modified elastomers.
[ 13 ]
In the polyphenylene ether resin composition according to the above [ 11 ] or [ 12 ],
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. Stuff.
[ 14 ]
A cured product obtained by curing the polyphenylene ether resin composition according to any one of the above [1] to [ 13 ].
[ 15 ]
A dry film comprising the polyphenylene ether resin composition according to any one of the above [1] to [ 13 ].
[ 16 ]
A film obtained by curing the dry film according to the above [ 15 ].
[ 17 ]
A prepreg containing the polyphenylene ether resin composition according to any one of the above [1] to [ 13 ] and a sheet-like fiber base material.
[ 18 ]
A metal-clad laminate obtained by laminating at least one selected from the dry film according to the above [ 15 ], the film according to the above [ 16 ], and the prepreg according to the above [ 17 ], and a metal foil.
[ 19 ]
An electrically insulating layer formed of at least one selected from the dry film according to the above [ 15 ], the film according to the above [ 16 ], and the prepreg according to the above [ 17 ], and provided on the electrically insulating layer. A printed wiring board with a conductor layer.
[ 20 ]
An electronic device provided with the printed wiring board according to the above [ 19 ].

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

Hereinafter, the present invention will be described based on the embodiments. In the present embodiment, "A to B" indicating the numerical range represent 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 the present embodiment contains 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 5 or more and 50 or less. It is preferably 5.2 or more and 20 or less, and more preferably 5.2 or more and 10 or less.
When (A) / (B) is equal to or more than the above lower limit value or exceeds the above lower limit value, it is possible to improve the thermal stability of the obtained cured product while satisfying good dielectric properties and heat resistance. Further, when (A) / (B) is not more than the above upper limit value, the dielectric property of the obtained cured product can be improved while satisfying good thermal stability and heat resistance.
From the above, when (A) / (B) is within the above range, a cured product having excellent heat resistance and thermal stability while satisfying the dielectric properties in the high frequency region suitable for the printed wiring board can be obtained. Is possible.

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

[Polyphenylene ether (A)]
As the polyphenylene ether (A) according to the present 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 the present embodiment is not particularly limited, but is preferably a modified polyphenylene ether terminally modified with a substituent having a carbon-carbon unsaturated bond.
The substituent having a carbon-carbon unsaturated bond is not particularly limited, and examples thereof include a substituent represented by the following formula (1).

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 to 10, Z represents an arylene group, and R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group.
Here, when n = 0 in the above formula (1), it indicates that Z is directly bonded to the terminal of the polyphenylene ether. Examples of the arylene group of Z include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group such as a naphthalene ring, and the hydrogen atom bonded to the aromatic ring is an alkenyl group, an alkynyl group or a formyl. It also includes derivatives substituted with functional groups such as groups, alkylcarbonyl groups, alkenylcarbonyl groups, or alkynylcarbonyl groups.

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) can be mentioned.

Examples of the other substituent having a carbon-carbon unsaturated bond include a (meth) acrylate group represented by the following formula (4).

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 7,000 or less from the viewpoint of better balancing the dielectric properties, adhesiveness, and heat resistance of the obtained cured product. Is more preferable, 1000 or more and 5000 or less is more preferable, and 1000 or more and 3000 or less is further preferable. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC).

Further, the polyphenylene ether (A) according to the present embodiment has a polyphenylene ether chain in the molecule, and for example, it is preferable that the polyphenylene ether (A) has 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 the above formula (5), m represents 1 to 50. Further, R ⁵ , R ⁶ , R ⁷ and R ⁸ are independent of each other and may be the same group or different groups, respectively. Further, 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.

The alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. More specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like can be mentioned.
The alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. More specifically, vinyl group, allyl group, 3-butenyl group and the like can be mentioned.
The alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. More specifically, an ethynyl group, a propa-2-in-1-yl group (propargyl group) and the like can be mentioned.

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but 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, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, cyclohexylcarbonyl group and the like can be mentioned.
The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but 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, acryloyl group, methacryloyl group, crotonoyl group and the like can be mentioned.
The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but 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 propioloyl group and the like can be mentioned.

Further, 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 is within the above-mentioned range. It is preferable to have. 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 the modified polyphenylene ether terminally modified by a substituent having a carbon-carbon unsaturated bond can be synthesized. For example, a method of reacting a polyphenylene ether in which the hydrogen atom of the terminal phenolic hydroxyl group is replaced with an alkali metal atom such as sodium or potassium with a compound represented by the following formula (6) can be mentioned.

In the above formula (6), as in the above formula (1), n represents an integer of 0 to 10, Z represents an arylene group, and R ^{1 to} R ³ independently represent a hydrogen atom or an alkyl group. Further, X represents a halogen atom, and specific examples thereof include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Of these, a chlorine atom is preferable.

The compound represented by the above formula (6) is not particularly limited, but for example, p-chloromethylstyrene or m-chloromethylstyrene is preferable.

Further, as the compound represented by the above formula (6), the above-exemplified compound may be used alone, or two or more kinds may be used in combination.

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 bifunctional phenol and trifunctional phenol, poly (2,6-dimethyl-1,4-phenylene oxide), etc. Examples thereof include those containing the polyphenylene ether as a main component. More specific examples of such polyphenylene ethers include polyphenylene ethers 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. Further, s is preferably 0 to 20, and t is preferably 0 to 20. That is, it is preferable that s indicates 0 to 20, t indicates 0 to 20, and the total of s and t indicates 1 to 30.

[Cyclic olefin (co) polymer (B)]
The cyclic olefin (co) polymer (B) according to the present embodiment is a (co) polymer having a repeating unit derived from the cyclic olefin as an essential constituent unit.
The cyclic olefin compound constituting the cyclic olefin (co) polymer (B) according to the present embodiment is not particularly limited, and examples thereof include the cyclic olefin monomers described in paragraphs 0037 to 0063 of International Publication No. 2006/0118261. be able to.

The cyclic olefin (co) polymer (B) according to the present embodiment has 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 preferably contains a repeating unit (b) derived from at least one cyclic olefin selected from the group consisting of the represented repeating units, and has good heat resistance and thermal stability of the obtained cured product, prepreg, and printed wiring substrate. It is represented by the following general formula (I) from the viewpoint that the dielectric property can be further improved while maintaining the above value, and the impregnation property of the polyphenylene ether resin composition into the sheet-like fiber base material or the like when producing the prepreg can be improved. A repeating unit (a) derived from at least one olefin, 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). It is more preferable to contain a repeating unit (b) derived from at least one cyclic olefin selected from the group consisting of repeating units.

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 above general formula (II), 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 ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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（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 above 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 an aliphatic hydrocarbon group or carbon 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. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 atoms, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and 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. It may form a monocyclic or polycyclic aromatic ring.

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

Further, the cyclic olefin (co) polymer (B) according to the present embodiment has heat resistance (particularly solder heat resistance) and heat resistance (particularly solder heat resistance) while maintaining good dielectric properties and thermal stability of the obtained cured product, prepreg, and printed wiring substrate. From the viewpoint of further improving the impregnation property of the sheet-shaped fiber base material, 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) are used. It is preferable that the repeating unit (c) derived from at least one non-conjugated diene olefin selected from the group consisting of the repeating units to be added is further contained, and is derived from the cyclic non-conjugated diene represented by the following general formula (VII). It is particularly preferred to include repeating units.

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 above 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 direct chain having 1 to 20 carbon atoms. It is a chain or branched hydrocarbon group and may contain double and / or triple bonds.

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 above general formula (VI), 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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 or different from each other, and have hydrogen atoms or carbon atoms 1 to 10. 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 above general formula (VII), 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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 combined with each other to form a monocyclic or polycyclic ring.

(Olefin monomer)
The olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin (co) polymer (B) according to the present embodiment, is addition-copolymerized to form a 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 above 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, and 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-eicosene 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.
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 the present embodiment. When the total number of moles with the repeating unit (c) derived from the monomer (c) having a crosslinkable double bond is 100 mol%, the ratio of the repeating unit (a) derived from the olefin is preferably 40 mol% or more and 90. It is 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 the above general formula (II), the above general formula (III) or It forms the repeating unit (b) derived from the cyclic olefin represented by the general formula (IV). Specifically, the cyclic olefins 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 above general formula (IIa), 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 ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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 or different from each other, and are an aliphatic hydrocarbon group or carbon 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. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 atoms, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and 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. It may form a monocyclic or polycyclic aromatic ring.

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

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

For 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 Pentadecadien 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 -Heneikosen derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivative, cyclopentadiene-acenaftylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, Examples thereof include 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivatives and cycloalkylene derivatives 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.

As the cyclic olefin monomer (b) represented by the above general formula (IIa), bicyclo [2.2.1] -2-heptene (also referred to as norbornene), tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene (also called tetracyclododecene) is preferably used, and tetracyclo [4.4.0.1 ^2,5 . It is more preferable to use 17 and ¹⁰ ] -3-dodecene. Since these cyclic olefins have a rigid ring structure, the elastic modulus of the copolymer and the cured product can be easily maintained, and since they do not contain a heterogeneous double bond structure, there is an advantage that cross-linking can be easily controlled.

Crosslinkability between 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 the present embodiment. When the total number of moles with 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 mol. % Or more and 50 mol% or less, more preferably 3 mol% or more and 45 mol% or less, still more preferably 5 mol% or more and 40 mol% or less.

(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) copolymer (B) according to the present embodiment, is additionally copolymerized and the above general formula (V). ), The above general formula (VI), or the repeating unit (c) derived from the non-conjugated diene olefin of the above general formula (VII). Specifically, the side chain portions represented by the general formulas (V), the general formula (VI), and the general formulas (Va), (VIa), and (VIIa) corresponding to the general formula (VII), respectively. A monomer (c) having a crosslinkable double bond is used.

In the above general formula (Va), 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 direct chain having 1 to 20 carbon atoms. It is a chain or branched hydrocarbon group and may contain double and / or triple bonds.

The linear polyene represented by the above general formula (Va) is not particularly limited, but is, 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. Further, a cyclizable polyene cyclized from a polyene such as 1,3-butadiene, 1,5-hexadiene may be used.

In the above general formula (VIa), 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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 or different from each other, and have hydrogen atoms or carbon atoms 1 to 10. R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocyclic or polycyclic ring.

The monomer (c) having a crosslinkable double bond in the side chain portion represented by the general formula (VIa) is not particularly limited, but is, for example, 5-ethylidene-2-norbornene, 5-n. -Propyridene-2-norbornene, 5-isopropylidene-2-norbornene, 5-ethylidene-6-methyl-2-norbornene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-Dodecene and the like. Of these, 5-ethylidene-2-norbornene is preferable.

In the above 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 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is 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 combined with each other to form a monocyclic or polycyclic ring.

The monomer (c) having a crosslinkable double bond in the side chain portion represented by the general formula (VIIa) is not particularly limited, but for example, it is crosslinked to the side chain portion represented by the following chemical formula. A monomer (c) having a sex double bond can be mentioned. Of these, 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

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

The repeating unit (a) derived from the olefin monomer, the repeating unit (b) derived from the cyclic olefin monomer (b), and the above side, which are contained in the cyclic olefin (co) polymer (B) according to the present embodiment. 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%, it is derived from the monomer (c) having a crosslinkable double bond in the side chain portion. The ratio of the repeating unit (c) is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 45 mol% or less, and further preferably 5 mol% or more and 40 mol% or less.

In particular, when the proportion 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 has more stable dielectric properties over time. It is even better and has excellent heat resistance. Further, 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 these physical properties can be obtained.
By setting the proportion of the structural unit (c) derived from the monomer (c) having a crosslinkable double bond in the side chain portion to the above upper limit or less, the moldability and solubility of the cyclic olefin (co) polymer (B) It is possible to further improve the stability of the dielectric properties of the cured product over time while improving the above. Further, by setting the ratio of the structural unit (c) derived from the monomer (c) having a crosslinkable double bond in the side chain portion to the above lower limit value or more, the heat resistance and mechanical properties of the cured product are further improved. be able to.

The number of double bonds per repeating unit (c) can be appropriately set depending on the intended use, but as the monomer (c) having a crosslinkable double bond in the side chain portion from which it is derived, from the viewpoint of reaction control and the like. From 5-Etylidene-2-norbornene, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . ^17,10 ] At least one diene compound selected from the group consisting of -3-dodecene and dicyclopentadiene is preferred, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4. 0.1 ^{2, 5} . ^{17 and 10} ] -3-dodecene and dicyclopentadiene are more preferred, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene is more preferred, and 5-vinyl-2-norbornene is particularly preferred.

The comonomer content and the glass transition temperature (Tg) of the cyclic olefin (co) polymer (B) according to the present embodiment can be controlled by the charging ratio of the monomers according to the intended use. The Tg of the cyclic olefin (co) polymer (B) according to the present embodiment is usually 50 ° C. or higher and 300 ° C. or lower, preferably 60 ° C. or higher and 250 ° C. or lower, and particularly preferably 70 ° C. or higher and 200 ° C. or lower. Is. When Tg is not more than the above upper limit value, the moldability of the cyclic olefin (co) polymer (B) can be further improved. Further, when Tg is at least the above lower limit value, the heat resistance and mechanical properties of the obtained cured product are improved.

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 contained in decalin at 135 ° C. The ultimate viscosity [η] measured in 1 above is, for example, 0.01 to 1.0 dl / g, preferably 0.05 to 0.7 dl / g, and more preferably 0.10 to 0.5 dl / g. Is.
The ultimate viscosity [η] of the cyclic olefin (co) polymer (B) can be controlled by the polymerization conditions such as the polymerization catalyst, the co-catalyst, the amount of H ₂ added, and the polymerization temperature.

Here, as the ring-opening polymer of the cyclic olefin, for example, a ring-opening polymer of a norbornene-based monomer and a ring-opening weight of the norbornene-based monomer and another monomer capable of ring-opening copolymerization thereof. Coalescence and these hydrides and the like can be mentioned.

Examples of the norbornene-based monomer include bicyclo [2.2.1] -2-heptene (common name: norbornene) and its derivatives (having a substituent on the ring), and tricyclo [4.3.01, 6]. .12,5] Deca-3,7-diene (trivial name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo [4.3.0.12.5] deca-3-ene (trivial name meteno) Tetrahydrofluorene: 1,4-methano-1,4,4a, 9a-also referred to as tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene (common name: tetracyclododecene) and its derivatives, and the like.
Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, an alkylidene group and the like. The substituent may have one or two or more. Examples of the derivative having a substituent on such a ring include 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-en and the like.
These norbornene-based 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 thereof, comprises a known ring-opening polymerization of a monomer component. It can be obtained by polymerization in the presence of a catalyst.
Examples of the ring-opening polymerization catalyst include a metal halide such as ruthenium and osmium, a catalyst composed of a nitrate or an acetylacetone compound and a reducing agent; and a metal halide or an acetylacetone compound such as titanium, zirconium, tungsten and molybdenum. , A catalyst composed of an organoaluminum compound; and the like can be used.
Examples of other monomers capable of ring-opening copolymerization with the norbornene-based monomer include monocyclic cyclic olefin-based monomers such as cyclohexene, cycloheptene, and cyclooctene.

The hydrogenated product of the ring-opened polymer of the norbornene-based monomer and the hydrogenated product of the ring-opened polymer of the norbornene-based monomer and other monomers capable of ring-opening copolymerization are usually described as described above. It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymer solution of the polymer 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, the method for producing a cyclic olefin (co) polymer described in paragraphs 0075 to 0219 of International Publication No. 2012/046443 and International Publication No. 2006 /. It can be produced according to the method for producing a cyclic olefin (co) polymer described in paragraphs 0995 to 0234 of No. 118261. Details are omitted here.

[Compatible agent (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) for compatibilizing the polyphenylene ether (A) and the cyclic olefin (co) polymer (B).
Examples of the compatibilizer (C) include modified polyolefins, modified elastomers, compounds having a polar group in the molecule and an unsaturated carbon bond capable of contributing to the polymerization reaction, and the like.

Examples of the modified polyolefin include polyolefins obtained by grafting or graft-polymerizing a monomer having a polar group, a copolymer of an olefin and a monomer having a polar group, and the like.
Among these, polyolefins grafted with a monomer having a polar group are preferable. Here, "graft" means introducing a compound having a polar group into a stem polymer which is a main chain. "Graft-polymerized" means introducing a branch polymer composed of a polymer different from the main chain into the stem polymer which is the main chain.

Examples of the polar group include an amino group, a hydroxyl group, a carboxyl group, an epoxy group, a nitrile group, a nitro group, an aldehyde group, an amide group, an ester group, an acid anhydride and the like. These are used alone or in combination of two or more. 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.

Examples of the monomer having such a polar group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, and butyl acrylate. Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylicamide, maleimide, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include propyl methacrylate, 2-hydroxypropyl acrylate, and oxazoline. The above compounds can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable.

The polyolefins include polyolefins such as polyethylene, polypropylene, ethylene / α-olefin copolymer, propylene / 1-butene copolymer, propylene / α-olefin copolymer, poly-4-methylpentene, and polybutene. Or oligomers, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, chlorosulfated polyethylene, ethylene vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, chlorine Examples thereof include polyethylene chemicals, styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers and the like. These can be used alone or in combination of two or more.

Examples of the polyolefin grafted with such 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-polymerizing a monomer having a polar group.
Examples of the polar group include an amino group, a hydroxyl group, a carboxyl group, an epoxy group, a nitrile group, a nitro group, an aldehyde group, an amide group, an ester group, an acid anhydride and the like. These are used alone or in combination of two or more. 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.

Examples of the monomer having such a polar group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, and butyl acrylate. Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylicamide, maleimide, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include propyl methacrylate, 2-hydroxypropyl acrylate, and oxazoline. The above compounds can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable.

Examples of the elastomer include a styrene / conjugated diene block copolymer resin (butadiene, isoprene, etc. as the conjugated diene), a hydrogenated additive of the styrene / conjugated diene block copolymer resin (butadiene, isoprene, etc. as the conjugated diene), and the like. Triblock copolymer resin of styrene / conjugated diene / styrene (butadiene, isoprene etc. as conjugated diene), hydrogenated additive of triblock copolymer resin of styrene / conjugated diene / styrene (butadiene, isoprene etc. as conjugated diene), etc. Styrene-based elastomers; natural rubber, polyisoprene rubber, polybutadiene rubber, nitrile rubber (acrylonitrile-butadiene copolymer), chloroprene rubber, butyl rubber, acrylic rubber, polyurethane elastomer, silicone rubber, epichlorohydrin rubber, nitrile isoprene rubber, etc. Synthetic rubber; polyester elastomer, urethane elastomer and the like can be mentioned. These can be used alone or in combination of two or more.

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

Further, the compatibilizer (C) is not limited to the above-mentioned polymer compounds typified by modified polyolefins and modified elastomers, and low molecular weight compounds having no repeating unit can be used.

As such a low molecular weight compound, a compound having a polar group in the molecule and an unsaturated carbon bond capable of contributing to the polymerization reaction is preferable. Examples of the polar group shown here include an amino group, a hydroxyl group, a carboxyl group, an epoxy group, a nitrile group, a nitro group, an aldehyde group, an amide group, an ester group and a glycidyl group. 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 the compound having a polar group and an unsaturated carbon bond capable of contributing to the polymerization reaction in the molecule, acrylic acid, methacrylic acid, or a derivative thereof is preferably used from the viewpoint of availability and the like.

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

Examples of compounds that can be used as the compatibilizer (C) are listed above, but these can be used alone or in combination of a plurality of types.
The content of the compatibilizer (C) is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass, when the polyphenylene ether (A) in the polyphenylene ether resin composition is 100 parts by mass. It is 2 parts by mass or more and 5 parts by mass or less, and particularly preferably 2 parts by mass or more and 5 parts by mass or less.

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

In the present embodiment, the method for producing the varnish may be any method, but usually includes a step of mixing the polyphenylene ether resin composition and the solvent. The order of mixing the components is not limited, and any method such as batch or division can be used. The device for preparing the varnish is not limited, and any device capable of stirring and mixing, a batch type, or a continuous type may be used. The temperature at which the varnish is prepared can be arbitrarily selected in the range from room temperature to the boiling point of the solvent.
A varnish may be prepared by using the reaction solution obtained when the cyclic olefin (co) polymer (B) is obtained as it is as a solvent and dissolving the polyphenylene ether (A) therein. Further, after purifying the cyclic olefin (co) polymer (B), a varnish may be prepared by separately adding a polyphenylene ether (A) and a solvent.

[Cured 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. The method for curing the polyphenylene ether resin composition is not particularly limited, and examples thereof include a method of curing the polyphenylene ether resin composition while molding it into an arbitrary shape using a radical polymerization initiator, an electron beam, or other radiation, or after molding. ..

For curing with a radical polymerization initiator, the usual curing method with a radical polymerization initiator applied for polyolefin can be applied as it is. That is, a radical polymerization initiator such as dicumylperoxide is mixed with the polyphenylene ether (A) and the cyclic olefin (co) polymer (B) according to the present 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 of the total of the polyphenylene ether (A) and the cyclic olefin (co) polymer (B), preferably 0.02 to 20 parts by mass. It is 0.05 to 10 parts by mass, more preferably 0.5 to 10 parts by mass. When the blending ratio of the radical polymerization initiator is not more than the above upper limit value, the dielectric property of the cured product can be improved, and when it is more than the above lower limit value, the heat resistance and mechanical properties of the cured product can be improved.

As the radical polymerization initiator, known thermal radical polymerization initiators, photoradical polymerization initiators, and these can be used in combination. 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 dicumylperoxide, t-butylcumylperoxide, 2,5-bis (t-butylperoxy) 2,5-dimethylhexane, and 2,5-bis (t-butylper). Oxy) Dialkyl peroxides such as 2,5-dimethylhexin-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, bis (α-t-butylperoxyisopropyl) benzene; 1 , 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) ballerate, ethyl-3,3-bis (t-butylperoxy) butylate, 3,3,6,6,9,9-hexamethyl-1,2 , 4,5-Tetraoxycyclononane and other peroxyketals; bis (t-butylperoxy) isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate and other peroxyesters; t-butyl Hydroperoxides such as hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthan hydroperoxide; Bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepan and the like can be mentioned.

Among the radical polymerization initiators, the photoradical polymerization initiator is specifically, for example, benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-. Examples thereof include on, benzophenone, methylbenzoylformate, isopropylthioxanthone and a mixture of two or more thereof. A sensitizer can also be used together with these photoradical polymerization initiators. Examples of sensitizers include anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p, p'-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranyl, nitrobenzene, p-dinitrobenzene, 2- Nitro compounds such as nitrofluorene, aromatic hydrocarbons such as anthracene and chrysen, sulfur compounds such as diphenyldisulfide, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene and the like. Nitro compounds and the like can be mentioned.

When the polyphenylene ether resin composition according to the present embodiment is cured with a radical polymerization initiator, the curing temperature is usually 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 120 to 250 ° C. May be changed stepwise to cure. When it is at least the above lower limit value, curing can proceed sufficiently. Further, when it is not more than the above upper limit value, coloring of the obtained cured product can be suppressed and the process can be simplified.

The method of curing using an electron beam or other radiation has an advantage that the temperature and fluidity at the time of molding are not restricted, and examples of radiation include γ-rays and UV in addition to electron beams. ..

Both the method using a radical polymerization initiator and the method of curing using radiation can be cured in combination with the cross-linking aid (D).

The cross-linking aid (D) is not particularly limited, but for example, oximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethyl propantri. Aacrylates 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. Allyl compounds such as: N, N'-m-phenylene bismaleimide, N, N'-(4,4'-methylenediphenylene) Maleimide compounds such as dimaleimide; vinyl norbornene, etilidennorbornene, dicyclopentadiene and the like. Cyclic non-conjugated diene; polybutadiene and the like can be mentioned. These cross-linking 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, and terminal urethane methacrylate-modified polybutadiene.

When the polyphenylene ether resin composition according to the present embodiment contains the cross-linking aid (D), the polyphenylene ether is obtained from the viewpoint of further improving the heat resistance of the obtained cured product 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, and the cross-linking aid (crosslinking aid ( 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 may contain, if necessary, a flame retardant, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an antifogging agent, a lubricant, and a dye. , Pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, thermoplastic resins and thermosetting resins other than polyphenylene ether (A) and cyclic olefin (co) polymer (B), etc. Can be blended to the extent that the above is not impaired, 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 and β- (3,5-di-t). -Butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamidbis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and other phenolic antioxidants; stearic acid Fatty acid metal salts such as zinc acid, calcium stearate, and calcium 12-hydroxystearate; polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, and pentaerythritol tristearate. .. These may be blended alone or in combination, eg, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate and Examples thereof include a combination with glycerin monostearate.

As the flame retardant, for example, an antimony flame retardant, a halogen flame retardant, and a phosphorus flame retardant can be used.
Examples of the antimony-based flame retardant include antimony oxide, antimony pentoxide, antimony tetroxide, and sodium antimonate.
As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance during molding, dispersibility in the resin, 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 [eg, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetra Brobromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether), etc.], tetrabromobisphenol S, and derivatives thereof [for example, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc.], tetrabromobisphenol anhydride, and derivatives thereof [for example, tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.], ethylenebis (5,6-dibromonorbornene-2, 3-Dicarboxyimide), Tris- (2,3-dibromopropyl-1) -isocyanurate, an adduct of the deal alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bistribromophenyl Ether, ethylenebispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis Bromine-based flame retardants such as (tribromophenyl) fumalamide and N-methylhexabromodiphenylamine; chlorine-based flame retardants such as chlorinated paraffin are preferably used.

Examples of the phosphorus-based 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 phosphates such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, etc. Ester flame retardant; aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyldiphenyl phosphate, dicredylphenyl phosphate, tricresylfuphosphate, trixylate Nylphosphate, xylenyldiphenyl phosphate, tri (isopropylphenyl) phosphate, isopropylphenyldiphenyl phosphate, diisopropylphenylphenyl phosphate, tri (trimethylphenyl) phosphate, tri (t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, octyldiphenyl phosphate. Non-propyl phosphate ester flame retardant such as aromatic phosphoric acid ester and the like can be mentioned.

Organic or inorganic fillers include silica, diatomaceous soil, alumina, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite. , Tarku, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, Examples include polyamide fibers.

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

The curing reaction can also be carried out in a molten state of a mixture of the polyphenylene ether resin composition according to the present embodiment and a compound involved in curing such as the above-mentioned radical polymerization initiator. Further, the mixture can be carried out in a solution state in which the mixture is dissolved or dispersed in a solvent, or the solvent is volatilized from the solution state dissolved in the solvent to form an arbitrary shape such as a film or a coating, and then the curing reaction is further promoted. You can also do it.

When the reaction is carried out in a molten state, a mixture of raw materials is melt-kneaded and reacted using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, or a continuous mixer. Further, the curing reaction can be further advanced after molding by an arbitrary method.

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

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

Since the cured product according to the present embodiment is excellent in solvent resistance, heat resistance, and mechanical strength, the molded product containing the cured product is a coating material for organic EL, a base film base material for a solar cell in the aerospace field, and the like. Coating materials for solar cells and thermal control systems, semiconductor elements, light emitting diodes, electronic elements such as various memories, hybrid ICs, MCMs, printed wiring boards, prepregs and laminates used to form insulating layers for printed wiring boards. It can be used as an overcoat material for display parts, an interlayer insulating material, a liquid crystal display, a substrate for a solar cell, and the like.
In particular, since 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 for forming an insulating layer of the high-frequency printed wiring board, a prepreg, etc. It can be suitably used for a laminate or the like.

[Dry film, film or sheet]
The polyphenylene ether resin composition according to the present embodiment can be molded into a dry film, film or sheet and used for various purposes. Various known methods can be applied as a method for forming a dry film, a film or a sheet using the polyphenylene ether resin composition according to the present embodiment. For example, a method of applying the above-mentioned varnish on a supporting base material such as a thermoplastic resin film, drying the varnish, and then heat-treating the polyphenylene ether resin composition to cure the polyphenylene ether resin composition can be mentioned. The method of applying the varnish to the supporting base material is not particularly limited, and examples thereof include coating using a spin coater, coating using a spray coater, and coating using a bar coater.
Further, a method of obtaining a dry film, a film or a sheet by melt-molding the polyphenylene ether resin composition of the present embodiment can also be mentioned.

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

[Prepreg]
Further, the prepreg according to the present embodiment is formed by synthesizing the polyphenylene ether resin composition of the present embodiment and the sheet-like fiber base material.
The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, a method including a step of impregnating the sheet-shaped fiber base material with the above-mentioned varnish to obtain an impregnated body and a step of heating the obtained impregnated body to dry the solvent contained in the varnish can be mentioned.
The sheet-shaped fiber base material is impregnated with the varnish by a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method. This can be done by applying it to a fiber substrate, overlaying a protective film on it if necessary, and pressing it from above with a roller or the like.
The step of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but for example, it is dried in air or nitrogen by a blower dryer in a batch type, or the heating furnace is operated in a continuous step. Examples include a method of drying by passing through.
In the present embodiment, after impregnating the sheet-shaped fiber base material with the varnish, the obtained impregnated body is heated to a predetermined temperature, so that the solvent contained in the varnish evaporates and a prepreg is obtained.

The fibers constituting the sheet-shaped fiber base material according to the present embodiment are not particularly limited, but for example, PET (polyethylene terephthalate) fibers, aramid fibers, polyamide (nylon) fibers, organic fibers such as liquid crystal polyester fibers; glass fibers, Inorganic fibers such as carbon fiber, alumina fiber, tungsten fiber, molybdenum fiber, titanium fiber, steel fiber, boron fiber, silicon carbide fiber, silica fiber: and the like can be mentioned. 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 preferably used.
The impregnation of the sheet-like fiber substrate with varnish is carried out, for example, by dipping and coating. The impregnation may be repeated a plurality of times if necessary.
These sheet-shaped fiber base materials can be used individually or in combination of two or more, and the amount used thereof is appropriately selected depending on the desire, but is usually 10 to 90 mass in the prepreg or the laminate. %, Preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass. Within this range, the dielectric properties of the obtained laminate and the mechanical strength are highly balanced, which is suitable.

The thickness of the prepreg according to the present embodiment is appropriately selected depending on the intended use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0. It is 5 mm. Within this range, properties such as shapeability at the time of lamination and mechanical strength and toughness of the laminated body obtained by curing are sufficiently exhibited and are suitable.

The dry film, film or prepreg according to the present embodiment may be made into a metal-clad laminate by laminating a metal foil on at least one surface and heat-curing it by a laminating press or the like.
Examples of the metal foil include copper foil, aluminum foil, nickel foil, gold foil, silver foil, stainless steel foil and the like.

[Printed circuit 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 manufacturing a printed wiring board, and the method is not particularly limited. For example, a dry film, film, sheet or prepreg manufactured by the above method is heat-cured by a laminated press or the like to form an electrically insulating layer. Form. Next, the conductor layer is laminated on the obtained electrically insulating layer by a known method to prepare a laminated body. After that, a printed wiring board can be obtained by circuit-processing or the like on the conductor layer in the laminated body.

As the metal to be the conductor layer, metals such as copper, aluminum, nickel, gold, silver, and stainless steel can be used. As a method for forming the conductor layer, in addition to the method of heat-sealing the metals to a cured product by making a foil or the like, a method of laminating with an adhesive or a method of sputtering, vapor deposition, plating or the like is used. It can be produced by the method of forming. As the aspect of the laminated body, either a single-sided plate or a double-sided plate may be used.

Such a printed wiring board can be used as an electronic device by mounting an electronic component such as a semiconductor element, for example. Electronic devices 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. , Smartphones, PHS, PDA, tablet terminals and other communication devices; personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, digital media players and other digital devices; 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 measuring devices, etc.; and the like.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

The composition and ultimate viscosity [η] of the cyclic olefin (co) polymer (B) used in Synthesis Examples, Examples and Comparative Examples were measured by the following methods.

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

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

The following raw materials were used in the experiment.

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

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

(Polyphenylene ether (A))
Polyphenylene ether (A-1): Modified polyphenylene ether synthesized according to Synthesis Example 1 below Polyphenylene ether (A-2): Modified polyphenylene ether (SABIC innovative) in which the terminal hydroxyl group of the polyphenylene ether of the above formula (7) is modified with a methacrylic group. SA9000 manufactured by Plastics Co., Ltd.)

(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): 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] = 0.42dl / g)

(Compatible agent (C))
Compatibility agent (C-1): Synthesized according to Synthesis Example 4 below.

(Other)
MMAO (manufactured by Tosoh Finechem)
MAO (manufactured by Nippon Aluminum Alkyls, Inc.)
5-Vinyl-2-Norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-Dodecene (manufactured by Mitsui Chemicals, Inc.)
Dikmyl peroxide (manufactured by NOF Corporation, Park Mill D)
Divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polybutadiene (manufactured by Nippon Soda, 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) of International Publication No. 2014/203511. Specifically, it is as follows.
100 g of polyphenylene ether oligomer (SA90 manufactured by SABIC), 15 g of chloromethylstyrene and 0.6 g of tetrabutylammonium bromide were added to a glass reactor charged with 200 g of toluene, and the mixture was heated to 75 ° C. with stirring to dissolve it. Then, 20 g of a 50 wt% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at 75 ° C. for 4 hours. Then, it was neutralized with hydrochloric acid, and methanol was added to precipitate the product. The precipitated product was washed with a solution of methanol and water 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)]
In a fully nitrogen-substituted SUS autoclave with an internal volume of 4 L, 1670 ml of xylene, 212 ml of 5-vinyl-2-norbornene (VNB), and tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] -3-Dodecene (TD) 120 ml, MMAO (manufactured by Tosoh Finechem Co., Ltd.) toluene solution 4 mmol in terms of Al, hydrogen 1984 ml, and then ethylene is added to the system until the total pressure reaches 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, the polymerization was carried out at 25 ° C. for 60 minutes, and then the polymerization was stopped by press-fitting 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 was added to precipitate the entire amount of the polymer, and the mixture was stirred and filtered through a filter paper. This operation was repeated until there were no reactants, and the obtained polymer was dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / TD / VNB copolymer. The ultimate 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)]
40 mL of toluene was charged into a fully nitrogen-substituted glass reactor, and the liquid and gas phases were saturated with nitrogen at a flow rate of 30 L / h. Next, tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] -3-dodecene (TD) 20.0 mL, 1-hexene 28.2 mL, and methylaluminoxane (MAO) were added in an amount of 10 mmol in terms of aluminum atoms. 0.010 mmol of the 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 put 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 the mixture was stirred and filtered through a glass filter. The polymer was dried under reduced pressure at 130 ° C. for 10 hours to obtain a TD / 1-hexene copolymer. The monomer composition in the polymer determined by the NMR analysis method 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 (Compatible Agent (C-1))]
Polystyrene / polybutadiene / polystyrene triblock copolymer hydrogenated additive (Clayton G1652, number average molecular weight: 8.5 × 10 ⁴ , styrene) in a glass autoclave with a capacity of 1.0 L equipped with a stirring blade. Content: 30% by mass) 105 g and 340 ml of dehydrated toluene 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 dit-butyl peroxide was dissolved in 40 ml of dehydrated toluene were prepared, and both solutions were prepared over 4 hours. It was dropped sequentially. After completion of the dropping, the reaction was carried out at 165 ° C. for 2 hours.
The amount of maleic anhydride graft of the obtained modified copolymer was measured by oxygen analysis and found to be 3.5% by mass.

[Examples 1 to 13 and Comparative Examples 1 to 6]
First, each component is 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 obtain a varnish-like polyphenylene ether resin composition (resin varnish), respectively. Prepared.

The obtained resin varnish was applied onto a release-treated PET film at a rate of 10 mm / sec, and then dried at 120 ° C. for 10 minutes in a blower dryer under a nitrogen stream. Then, the temperature was raised to 200 ° C. and heated for 2 hours to obtain films made of crosslinked products. Next, the obtained film was peeled off from the PET film, and the following dielectric loss tangent, heat resistance and thermal stability were evaluated. The results obtained are shown in Tables 1 and 2, respectively.

(1) Heat resistance As an index of heat resistance, the storage elastic modulus (E') at 250 ° C. was measured. The measurement was carried out using RSA-III (manufactured by TA-Instruments) under nitrogen, scanning a frequency of 1 Hz, a strain of 0.1, and a temperature range of 25 ° C. to 300 ° C. at a heating rate of 3 ° C./min. For the measurement, a test piece cut out from the obtained film to a length of 50 mm and a width of 5 mm was used. 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 〇: 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 in the solder heat resistance test that no appearance abnormality occurs.

(2) Dissipation Factor The dielectric loss tangent of the film at 12 GHz was measured by the cylindrical cavity resonator method. Specifically, a network analyzer (8510B manufactured by YHP), a synthesized sweeper (8340B manufactured by YHP), and a test set (8515A) were used to measure the dielectric loss tangent of the film at 12 GHz.

(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, the polyphenylene ether (A), the cyclic olefin (co) polymer (B), the compatibilizer (C), the radical polymerization initiator, and the cross-linking aid (D) are blended in the blending ratios shown in Table 3 (in the table). The numerical values indicate parts by mass), and the mixture was added to toluene and mixed to prepare a varnish-like polyphenylene ether resin composition (resin varnish).

(Making prepreg)
Next, the obtained polyphenylene ether resin composition varnish was impregnated in a glass cloth (manufactured by Arisawa Mfg. Co., Ltd., 1031NT S640) and dried in a blower dryer at 120 ° C. for 10 minutes to obtain 0.1 mm thick prepregs. Made.

(Preparation of laminate)
Eight prepregs cut into 150 mm squares were stacked and heated with a vacuum press at a pressure of 3.5 MPa and 200 ° C. for 2 hours to prepare laminated bodies.
The following dielectric loss tangent evaluations were performed on the obtained laminates. The results obtained are shown in Table 3.

(Manufacturing of copper-clad laminate)
Eight prepregs cut into 150 mm squares are stacked, copper foils (F1-WS manufactured by Furukawa Denki Kogyo Co., Ltd.) are stacked on both sides, and heated 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 adhered were produced.
The following solder heat resistance and peel strength were evaluated for the obtained copper-clad laminate. The results obtained are shown in Table 3.

(1) Dissipation Factor The dielectric loss tangent of the laminate at 12 GHz was measured by the cylindrical cavity resonator method. Specifically, a network analyzer (8510B manufactured by YHP), a synthesized sweeper (8340B manufactured by YHP), and a test set (8515A) were used to measure the dielectric loss tangent of the laminate at 12 GHz.

(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 swelling did not occur ×: At least one of deformation and swelling occurred

(3) Peel strength Based on JIS C6481, the copper foil was peeled off from the copper-clad laminate, and the peeling strength at that time was measured.
Those having an intensity of 0.4 kN / m or more were evaluated as ◯, and those having an intensity of less than 0.4 kN / m were evaluated as x.

As can be seen from Table 1, the films of Examples 1 to 13 were found to be excellent in heat resistance and thermal stability while satisfying the dielectric properties in the high frequency region suitable for the printed wiring board. Further, it was found that the laminate and the copper-clad laminate of Example 14 were excellent in heat resistance and adhesiveness while satisfying the dielectric properties in the high frequency region suitable for the printed wiring board.
On the other hand, Comparative Examples 1, 2 and 7 containing no cyclic olefin (co) polymer (B) have a high dielectric loss tangent and inferior dielectric properties, and a large proportion of the cyclic olefin (co) polymer (B). 3 to 6 had a low dielectric loss tangent and excellent dielectric properties, but were inferior in thermal stability.

Claims (20)

A polyphenylene ether resin composition containing a polyphenylene ether (A) and a cyclic olefin (co) polymer (B).
The ratio ((A) / (B)) of the content (mass) of the polyphenylene ether (A) to the content of the cyclic olefin (co) polymer (B) in the polyphenylene ether resin composition exceeds 5. It der below,
A polyphenylene ether resin composition, wherein the polyphenylene ether (A) contains a modified polyphenylene ether modified by a substituent having a carbon-carbon unsaturated bond . In the polyphenylene ether resin composition according to claim 1,
The cyclic olefin (co) polymer (B)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
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 containing the derived repeating unit (b).

(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.)

(In the above 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 identical to each other. However, they may be different, such as hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.)

(In the above 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 or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. There, 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 directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, 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 or different from each other, and represent 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 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. .. 1 ^{7, 10} ] A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from -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 unit represented by the following general formula (VII). A polyphenylene ether resin composition further containing a repeating unit (c) derived from at least one non-conjugated diene olefin selected from the group consisting of units.

(In the above 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 has 1 to 20 carbon atoms. It is a straight or branched hydrocarbon group and may contain double and / or triple bonds.)

(In the above 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 identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ~ 20 aromatic hydrocarbon groups, R ¹⁰² and R ¹⁰³ may be the same or different from each other, are hydrogen atoms or alkyl groups with 1 to 10 carbon atoms, and R ⁷⁵ and R ⁷⁶ are bonded to each other. It may form a monocyclic ring or a polycyclic ring.)

(In the above 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 identical to each other. However, they may be different, such as hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. ~ 20 aromatic hydrocarbon groups, R ¹⁰⁴ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. May form a monocyclic ring or a polycyclic ring.) In the polyphenylene ether resin composition according to claim 4,
The repeating unit (c) derived from the non-conjugated diene olefin in the cyclic olefin (co) polymer (B) is a polyphenylene ether containing 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 . 1 ^{7, 10} ] A polyphenylene ether resin composition which is a repeating unit derived from at least one compound selected from -3-dodecene. In the polyphenylene ether resin composition according to any one of claims 1 to 6.
A polyphenylene ether resin composition in which the intrinsic viscosity [η] of the cyclic olefin (co) polymer (B) in decalin at 135 ° C. is 0.01 dl / g or more and 1.0 dl / g or less. In the polyphenylene ether resin composition according to any one of claims 1 to 7 .
A polyphenylene ether resin composition further containing a cross-linking aid (D). In the polyphenylene ether resin composition according to claim 8 .
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.
A polyphenylene ether resin composition having a content of the cross-linking aid (D) of 5 parts by mass or more and 50 parts by mass or less. In the polyphenylene ether resin composition according to any one of claims 1 to 9 .
A polyphenylene ether resin composition having a number average molecular weight of the polyphenylene ether (A) of 500 or more and 7,000 or less. In the polyphenylene ether resin composition according to any one of claims 1 to 10 .
A polyphenylene ether resin composition further containing a compatibilizer (C) for compatibilizing the polyphenylene ether (A) and the cyclic olefin (co) polymer (B). In the polyphenylene ether resin composition according to claim 11 .
A polyphenylene ether resin composition in which the compatibilizer (C) contains at least one selected from a modified polyolefin and a modified elastomer. In the polyphenylene ether resin composition according to claim 11 or 12 .
The polyphenylene ether resin composition in which the content of the compatibilizer (C) is 0.1 part 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. Stuff. A cured product obtained by curing the polyphenylene ether resin composition according to any one of claims 1 to 13 . A dry film comprising the polyphenylene ether resin composition according to any one of claims 1 to 13 . A film obtained by curing the dry film according to claim 15 . A prepreg containing the polyphenylene ether resin composition according to any one of claims 1 to 13 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 15 , the film according to claim 16 , and the prepreg according to claim 17 , and a metal foil. An electrically insulating layer formed of at least one selected from the dry film according to claim 15 , the film according to claim 16 , and the prepreg according to claim 17 , and a conductor provided on the electrically insulating layer. A printed wiring board with layers. An electronic device comprising the printed wiring board according to claim 19 .