JP6810621B2 - Resin composition and its crosslinked product - Google Patents

Description

The present invention relates to a resin composition and a crosslinked product thereof.

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, in order to reduce transmission loss at high frequencies to the utmost limit, a material for a circuit board having high insulation and small dielectric loss tangent is required.

Examples of the resin material used for such a circuit board include cyclic olefin copolymers obtained by copolymerizing diene described in Patent Document 1 and Patent Document 2.

Patent Document 1 and Patent Document 2 disclose that a sheet obtained by cross-linking a cyclic olefin copolymer copolymerized with a specific diene compound with an organic peroxide or the like exhibits excellent dielectric properties. ..
Further, Patent Document 3 discloses a resin composition containing a cyclic olefin copolymer copolymerized with a specific diene compound and various resins.
Further, Patent Document 4 describes a metal resin laminate including a resin layer and a metal foil layer provided on one side or both sides of the resin layer, and the resin layer is a norbornene-based copolymer of norbornene and α-olefin. The above-mentioned norbornene-based copolymer containing a polymer has a glass transition temperature of 250 ° C. or higher and 310 ° C. or lower, and a polystyrene-equivalent weight average molecular weight measured by gel permission chromatography of 5,000 or more and 300,000 or less. A metal resin laminate having a specific dielectric constant of 2.3 or less at 5 GHz and a dielectric tangent of 4 × 10 ^-4 or less of the above-mentioned norbornene-based copolymer is described.

Japanese Unexamined Patent Publication No. 2010-100843 International Publication No. 2012/044644 JP 2015-067822 JP-A-2016-037045

According to the studies by the present inventors, in order to use the crosslinked product obtained from the cyclic olefin copolymers described in Patent Documents 1 to 4 as a material for a circuit board, heat resistance and heat resistance are further maintained while maintaining dielectric properties. It became clear that the mechanical strength needed to be improved.

The present invention has been made in view of the above circumstances, and as materials for a circuit board, an interlayer insulating film for a circuit board for a highly integrated arithmetic unit (also referred to as an interlayer insulating layer in the circuit board) and a circuit board. It is an object of the present invention to provide a resin composition capable of obtaining a crosslinked body having excellent dielectric properties, heat resistance and mechanical properties in a high frequency region suitable for the above.

As a result of diligent studies to solve the above problems, the present inventors have added polyphenylene ether, polyimide resin, polyurethane, polyetheretherketone, polybutylene terephthalate, liquid crystal polymer, maleimide in a specific ratio to a specific cyclic olefin copolymer. By mixing one or more resins selected from the group consisting of resins and polybutadiene resins, while satisfying the dielectric properties in the high frequency region required for interlayer insulating films for circuit boards, circuit boards, etc. We have found that heat resistance and mechanical strength 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。）
［２］
［１］に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
下記一般式（Ｖ）で表される繰り返し単位、下記一般式（ＶＩ）で表される繰り返し単位および下記一般式（ＶＩＩ）で表される繰り返し単位からなる群から選ばれる少なくとも１種の非共役ジエン系オレフィン由来の繰り返し単位（ｃ）の含有量が０．０５モル％以下である樹脂組成物。

（上記一般式（Ｖ）において、Ｒ^２０１からＲ^２０６は互いに同一でも異なっていてもよく、水素原子、または炭素原子数１〜２０の炭化水素基であり、Ｐは炭素原子数１〜２０の直鎖または分岐状の炭化水素基で、二重結合および／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。）
［３］
［１］または［２］に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中の前記α−オレフィン由来の繰り返し単位（ａ）が、前記一般式（Ｉ）においてＲ^３００が炭素原子数２以上１０以下の直鎖状の炭化水素基である繰り返し単位を含む樹脂組成物。
［４］
［１］乃至［３］のいずれか一項に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中の前記環状オレフィン由来の繰り返し単位（ｂ）が、ビシクロ［２．２．１］−２−ヘプテンおよびテトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位である樹脂組成物。
［５］
［１］乃至［４］のいずれか一項に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
前記環状オレフィン由来の繰り返し単位（ｂ）の含有量が１０モル％以上９０モル％以下である樹脂組成物。
［６］
［１］乃至［５］のいずれか一項に記載の樹脂組成物において、
耐熱安定剤、耐候安定剤、耐放射線剤、可塑剤、滑剤、離型剤、核剤、摩擦磨耗性向上剤、難燃剤、発泡剤、帯電防止剤、着色剤、防曇剤、アンチブロッキング剤、耐衝撃剤、表面ぬれ改善剤、充填材、塩酸吸収剤、金属不活性化剤および硬化促進剤からなる群から選択される一種または二種以上の添加剤をさらに含む樹脂組成物。
［７］
［１］乃至［６］のいずれか一項に記載の樹脂組成物と溶媒を含有するワニス。
［８］
［１］乃至［６］のいずれか一項に記載の樹脂組成物の架橋体。
［９］
［８］に記載の架橋体を含むフィルムまたはシート。
［１０］
［９］に記載のフィルムまたはシートを基材に積層した積層体。
［１１］
［８］に記載の架橋体を含む電気絶縁層と、前記電気絶縁層上に設けられた導体層とを含む回路基板。
［１２］
［１１］に記載の回路基板を備えた電子機器。
［１３］
［１］乃至［６］のいずれか一項に記載の樹脂組成物とシート状繊維基材とを含むプリプレグ。
［１４］
［１］乃至［６］のいずれか一項に記載の樹脂組成物が表層に厚み１００μｍ以下で形成された多層成形体または多層積層フィルム。 [1]
One or more selected from the group consisting of cyclic olefin copolymer (P) and polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. A resin composition containing a resin (Q).
The mass ratio ((Q) / (P)) of the content of the resin (Q) to the content of the cyclic olefin copolymer (P) in the resin composition is 0.1 or more and 5 or less.
The cyclic olefin copolymer (P) is
The repeating unit (a) derived from at least one α-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 resin composition containing the derived repeating unit (b) .
A resin composition in which the resin (Q) contains polyphenylene ether.

(In the above general formula (I), R ³⁰⁰ represents 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. .)
[2]
In the resin composition according to [ 1 ],
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
At least one non-conjugated unit selected from the group consisting of a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating unit represented by the following general formula (VII). A resin composition in which the content of the repeating unit (c) derived from a diene-based olefin is 0.05 mol% or less.

(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.)
[3]
In the resin composition according to [1] or [2] ,
The repeating unit (a) derived from the α-olefin in the cyclic olefin copolymer (P) is a linear hydrocarbon group having R ³⁰⁰ having 2 or more and 10 or less carbon atoms in the general formula (I). A resin composition containing a repeating unit.
[4]
In the resin composition according to any one of [1] to [ 3 ],
The repeating unit (b) derived from the cyclic olefin in the cyclic olefin copolymer (P) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] -3-A resin composition which is a repeating unit derived from at least one compound selected from dodecene.
[5]
In the resin composition according to any one of [1] to [ 4 ],
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
A resin composition in which the content of the repeating unit (b) derived from the cyclic olefin is 10 mol% or more and 90 mol% or less.
[6]
In the resin composition according to any one of [1] to [ 5 ],
Heat-resistant stabilizer, weather-resistant stabilizer, radiation-resistant agent, plasticizer, lubricant, mold release agent, nucleating agent, friction abrasion improver, flame retardant, foaming agent, antistatic agent, colorant, antifogging agent, anti-blocking agent A resin composition further comprising one or more additives selected from the group consisting of impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbents, metal deactivators and curing accelerators.
[7]
A varnish containing the resin composition and solvent according to any one of [1] to [ 6 ].
[8]
The crosslinked product of the resin composition according to any one of [1] to [ 6 ].
[9]
A film or sheet containing the crosslinked product according to [ 8 ].
[10]
A laminate obtained by laminating the film or sheet according to [ 9 ] on a base material.
[11]
A circuit board including an electrically insulating layer including the crosslinked body according to [ 8 ] and a conductor layer provided on the electrically insulating layer.
[12]
An electronic device provided with the circuit board according to [ 11 ].
[13]
A prepreg containing the resin composition according to any one of [1] to [ 6 ] and a sheet-like fiber base material.
[14]
A multilayer molded product or a multilayer laminated film in which the resin composition according to any one of [1] to [ 6 ] is formed on the surface layer with a thickness of 100 μm or less.

According to the present invention, it is possible to obtain an interlayer insulating film for a circuit board for a highly integrated arithmetic unit and a crosslinked body having excellent dielectric properties, heat resistance and mechanical properties in a high frequency region suitable for a circuit board or the like. A possible resin composition can be provided.
Further, according to the present invention, by using the above resin composition, a crosslinked body, a film or a sheet, a laminated body, a circuit board, a multilayer molded product or a multilayer laminated film, a prepreg and an electronic device suitable as a material for a circuit board are provided. can do.

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.

First, the resin composition of the embodiment according to the present invention will be described.
The resin composition according to the present embodiment comprises a group consisting of a cyclic olefin copolymer (P), a polyphenylene ether, a polyimide resin, a polyurethane, a polyether ether ketone, a polybutylene terephthalate, a liquid crystal polymer, a maleimide resin, and a polybutadiene resin. Includes one or more selected resins (Q). The mass ratio ((Q) / (P)) of the content of the resin (Q) to the content of the cyclic olefin copolymer (P) in the resin composition is 0.1 or more and 5 or less. It is preferably 0.2 or more and 3 or less, more preferably 0.2 or more and 2 or less, and particularly preferably 0.2 or more and 1.5 or less.
When (Q) / (P) is at least the above lower limit value, the heat resistance of the obtained crosslinked body can be improved while satisfying good dielectric properties and mechanical strength. Further, when (Q) / (P) is not more than the above upper limit value, the dielectric property and mechanical strength of the obtained crosslinked body can be improved while satisfying good heat resistance.
From the above, when (Q) / (P) is within the above range, the dielectric properties and heat resistance in a high frequency region suitable for interlayer insulating films for circuit boards for highly integrated arithmetic units and circuit boards, etc. In addition, it is possible to obtain a crosslinked product having excellent mechanical properties.

Hereinafter, each component will be specifically described.

[Cyclic olefin copolymer (P)]
The cyclic olefin copolymer (P) according to the present embodiment is a copolymer having a repeating unit derived from the cyclic olefin as an essential constituent unit.
The cyclic olefin compound constituting the cyclic olefin copolymer (P) 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. it can.

The cyclic olefin copolymer (P) according to the present embodiment can control the glass transition temperature (Tg) by, for example, the type of monomer and the charging ratio of the monomer. The Tg of the cyclic olefin copolymer (P) according to the present embodiment is preferably 150 ° C. or higher and lower than 250 ° C., more preferably 170 ° C. or higher and lower than 230 ° C., and further preferably 180 ° C. or higher and lower than 220 ° C. .. When Tg is less than the above upper limit value, the processability of the cyclic olefin copolymer (P) can be further improved. Further, when Tg is at least the above lower limit value, the heat resistance and mechanical properties of the obtained insulating layer are improved.
Here, the Tg of the cyclic olefin copolymer (P) in the present embodiment is a value measured in a state before cross-linking with a cross-linking agent.

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

Further, the cyclic olefin copolymer (P) according to the present embodiment has the following general formula (I) from the viewpoint of further improving processability, solder heat resistance, dielectric properties and impregnation property into the sheet-like fiber base material. It is more preferable to include a repeating unit (a) derived from at least one α-olefin represented and a repeating unit (b) derived from at least one cyclic olefin represented by the following general formula (II). ..
Further, the cyclic olefin copolymer (P) according to the present embodiment is represented by the following general formula (V) when the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%. Repeat unit (c) derived from at least one non-conjugated diene olefin selected from the group consisting of a repeating unit represented by the following general formula (VI) and a repeating unit represented by the following general formula (VII). ) Is, for example, preferably 0.05 mol% or less, more preferably 0.01 mol% or less, from the viewpoint of improving the glass transition temperature of the cyclic olefin copolymer (P).

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

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

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

In the 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 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.

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、二重結合および／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 hydrogen atoms or hydrocarbon groups 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, 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 copolymer (P) 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は炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。環状オレフィン共重合体（Ｐ）のガラス転移温度を向上させ、得られる絶縁層の耐熱性をより向上させる観点から、Ｒ^３００は炭素原子数２以上１０以下の直鎖状または分岐状の炭化水素基が好ましく、炭素原子数２以上１０以下の直鎖状の炭化水素基がより好ましく、炭素原子数４以上１０以下の直鎖状の炭化水素基がさらに好ましい。
具体的には、Ｒ^３００が炭素原子数２以上１０以下の直鎖状または分岐状の炭化水素基である上記一般式（Ｉａ）で表されるオレフィンモノマーとしては、１−ブテン、１−ペンテン、１−へキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−へキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−へキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン等が挙げられる。中でも、１−ヘキセン、１−オクテン、１−デセンが好ましい。

In the above general formula (Ia), R ³⁰⁰ represents a linear or branched hydrocarbon group having 1 to 29 carbon atoms. From the viewpoint of improving the glass transition temperature of the cyclic olefin copolymer (P) and further improving the heat resistance of the obtained insulating layer, R ³⁰⁰ is a linear or branched hydrocarbon having 2 to 10 carbon atoms. The group is preferable, a linear hydrocarbon group having 2 or more and 10 or less carbon atoms is more preferable, and a linear hydrocarbon group having 4 or more and 10 or less carbon atoms is further preferable.
Specifically, 1-butene and 1-pentene are examples of the olefin monomer represented by the above general formula (Ia) in which R ³⁰⁰ is a linear or branched hydrocarbon group having 2 or more and 10 or less carbon atoms. , 1-Hexene, 3-Methyl-1-butene, 3-Methyl-1-pentene, 3-Ethyl-1-pentene, 4-Methyl-1-pentene, 4-Methyl-1-hexene, 4,4 Examples thereof include −dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene and 1-dodecene. Of these, 1-hexene, 1-octene, and 1-decene are preferable.

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

(Cyclic olefin monomer (b))
The cyclic olefin monomer (b), which is one of the copolymerization raw materials of the cyclic olefin copolymer (P) according to the present embodiment, is addition-copolymerized to form the general formula (II), the general formula (III), or the general formula (III). It forms a repeating unit (b) derived from a cyclic olefin represented by the 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 olefin monomer represented by the general formula (Ia) described above and the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component, the cyclic olefin can be used together. Since the solubility of the polymer (P) 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-acenaphthylene derivative, 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 . 1 ^7,10] -3-dodecene (also referred to as tetracyclododecene.) Is preferably used, tetracyclo [4.4.0.1 ^{2, 5.} It is more preferable to use ^17,10 ] -3-dodecene. Since these cyclic olefins have a rigid ring structure, the elastic modulus of the copolymer and the insulating layer 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.

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

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

The cyclic olefin copolymer (P) 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. 2012/044643 and International Publication No. 2006/118261. It can be produced according to the method for producing a cyclic olefin (co) polymer described in paragraphs 0995 to 0234 of the above. Details are omitted here.

[Resin (Q)]
The resin (Q) according to the present embodiment is one or two selected from the group consisting of polyphenylene ether, polyimide resin, polyurethane, polyetheretherketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. The above can be mentioned. Among these, polyphenylene ether is preferable from the viewpoint of further improving the performance balance of the dielectric property, heat resistance and mechanical strength of the obtained crosslinked product.

As the polyphenylene ether 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 according to the present embodiment is not particularly limited, but is preferably 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. It is more preferably 1000 or more and 5000 or less, and further preferably 1000 or more and 3000 or less. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC).

Further, the polyphenylene ether according to the present embodiment has a polyphenylene ether chain in the molecule, and for example, it is preferable that the polyphenylene ether 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 specifically, 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.

The polyimide resin according to the present embodiment is not particularly limited, and for example, those described in paragraphs 0008 to 0011 of JP2009-1220696A can be used.
More specifically, it is as follows.

The polyimide resin according to the present embodiment can be obtained, for example, by reacting a tetracarboxylic dianhydride, diimide or monoimide (hereinafter, abbreviated as a tetracarboxylic dianhydride or the like) with a diamine. The reaction between the anhydride of the tetracarboxylic acid and the like and the diamine can be carried out by using a generally known method. Further, as the polyimide resin according to this embodiment, a commercially available product can also be used.
Further, as the polyimide resin according to the present embodiment, linear polyimide is preferable.
Examples of the tetracarboxylic dianhydride include maleic acid, trimellitic acid, pyromeritic acid, anhydrides such as bis (3,4-dicarboxyphenyl) ether, and diimide or monoimide. Among these, diimide tetracarboxylic acid is preferable, and bismaleimide is particularly preferable.

The bismaleimide is not particularly limited, but for example, bis (4-maleimidephenyl) methane, N, N'-ethylene-bisimide maleate, N, N'-hexamethylene-bisimide maleate, N, N'maleate. -Metaphenylene-bisimide, N, N'-4,4'-diphenylmethane-bisimide (N, N'-methylenebis (also called -N-phenylmaleimide), N, N'-4,4'-maleate- Diphenyl ether-bisimide, N, N'-4,4'-diphenylsulfone-bisimide, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane-bisimide, maleic acid 4,4 '-Methylene-di-2,6-diisopropylaniline-bisimide and the like can be mentioned, and these can be used alone or in combination.

The diamine is not particularly limited, but for example, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, and the like. Metaphenylenediamine, 4,4'-diaminodiphenylmethane, bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 1,3-bis (2-p-anilinopropyridene) benzene, 1,4 -Bis (2-p-anilinopropyridene) benzene, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, dicyandiamide, acetoguanamine, benzoguanamine, m-toluylene diamine, 2 , 4-Diamino-6- (2'-Undecylimidazolyl- (1')-) ethyl-S-triazine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis Examples thereof include (3-aminophenoxy) benzene, bis-4- (4-aminophenoxy) phenylsulfone, and bis-4- (3-aminophenoxy) phenylsulfone. These can be used alone or in combination.
The diamine is preferably reacted with a tetracarboxylic acid anhydride or the like at a ratio of 0.3 to 1.2 mol of the diamine per mol of the tetracarboxylic acid anhydride or the like, preferably 0.5 to 1.0 mol. It is more preferable to react at a ratio.

The liquid crystal polymer according to the present embodiment is not particularly limited, and for example, those described in paragraphs 0023 to 0029 of JP-A-2008-19400 can be used.
More specifically, it is as follows.

The liquid crystal polymer according to the present embodiment refers to a melt-processable polymer having a property of forming an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope, and the molten sample placed on the Leitz hot stage can be observed at a magnification of 40 times under a nitrogen atmosphere. When the liquid crystal polymer according to the present embodiment is inspected between orthogonal polarizers, polarized light is normally transmitted even in a molten stationary state and exhibits optical anisotropy.

The liquid crystal polymer according to the present embodiment is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide, and the range includes a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain. It is in. These have a logarithmic viscosity (IV) of preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. ) Is used.

The aromatic polyester or aromatic polyester amide as the liquid crystal polymer according to the present embodiment contains at least one compound selected from the group of aromatic hydroxycarboxylic acid, aromatic hydroxyamine, and aromatic diamine as a constituent component. Aromatic polyesters and aromatic polyester amides having are particularly preferred.

More specifically
(1) Polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly (a) one or more kinds of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more kinds of aromatic dicarboxylic acids, aliphatic dicarboxylic acids and derivatives thereof, ( c) Polyester consisting of at least one or more of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof;
(3) Mainly (a) one or more kinds of aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more kinds of aromatic hydroxyamines, aromatic diamines and derivatives thereof, and (c) A polyester amide consisting of one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof;
(4) Mainly (a) one or more kinds of aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more kinds of aromatic hydroxyamines, aromatic diamines and derivatives thereof, and (c) One or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and (d) at least one or more of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof. Examples thereof include a polyester amide composed of. Further, a molecular weight modifier may be used in combination with the above-mentioned constituent components as needed.

Preferred examples of the specific compound constituting the liquid crystal polymer according to the present embodiment include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 2,6-dihydroxynaphthalene, and 1 , 4-Dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, aromatic diols such as compounds represented by the following formulas (I) and (II); terephthalic acid, isophthalic acid, 4,4'. Aromatic dicarboxylic acids such as −diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine can be mentioned.

（ただし、Ｘ：アルキレン（Ｃ１〜Ｃ４）、アルキリデン、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、−ＣＯ−より選ばれる基、Ｙ：−（ＣＨ_２）_ｎ−（ｎ＝１〜４）、−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）より選ばれる基である。）

(However, a group selected from X: alkylene (C1 to C4), alkylidene, -O-, -SO-, -SO _2- , -S-, and -CO-, Y:-(CH ₂ ) _n- (n). = 1 to 4), -O (CH ₂ ) _n O- (n = 1 to 4).)

The maleimide resin according to this embodiment is not particularly limited, and for example, those described in paragraphs 0009 to 0013 of JP-A-2006-124494 can be used.
More specifically, it is as follows.

The maleimide resin according to the present embodiment is not particularly limited as long as it is a maleimide resin obtained from the maleimide compound (X) having two or more maleimide groups in one molecule.

Examples of the maleimide compound (X) include bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, and bis (3,5-dimethyl-4-maleimide). Benzene) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, 2,2'-bis [4- (4-maleimidephenoxy) ) Benzene] Propane, polyphenylmethanemaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1 , 3-Phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) Benzene, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, polytetramethyleneoxide-bis (4-maleimidebenzoate), etc. Can be mentioned. These may be used alone or in combination of two or more. Further, a prepolymer of a maleimide compound (X) or a prepolymer of a maleimide compound (X) and an amine compound can also be used.

The maleimide resin according to the present embodiment also includes, for example, a mixture (also referred to as bismaleimide triazine resin) of a maleimide resin and a triazine resin obtained by reacting a maleimide compound (X) and a cyanate ester compound (Y). included.

Here, the cyanate ester compound (Y) is not particularly limited as long as it is a cyanate ester compound having two or more cyanate groups in one molecule, for example.

Examples of the cyanate ester compound (Y) include 1,3- or 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-, 1,4-, 1,6-. , 1,8-, 2,6- or 2,7-disyanate naphthalene, 1,3,6-tricyanate naphthalene, 4,4-disyanate biphenyl, bis (4-cyanate phenyl) methane, bis (3, 5-Dimethyl-4-Cyanatephenyl) methane, 2,2-bis (4-Cyanatephenyl) propane, 2,2-bis (3,5-dibromo-4-yanatephenyl) propane, 2,2-bis (3) , 5-Dimethyl-4-Cyanatephenyl) Propane, Bis (4-Cyanatephenyl) Ether, Bis (4-Cyanatephenyl) Thioether, Bis (4-Cyanatephenyl) Sulfon, Tris (4-Cyanatephenyl) Phosphite, Tris Dicyclo is a cyanate ester compound obtained by reacting (4-cyanate phenyl) phosphate, oligomers (novolac, hydroxyl group-containing thermoplastic resin (hydroxypolyphenylene ether, hydroxypolystyrene, hydroxypolycarbonate, etc.)) with cyanate halide. Examples thereof include a cyanate ester compound obtained by reacting a polyfunctional phenol bonded with pentadiene with cyanate halide. These may be used alone or in combination of two or more.

The polybutadiene resin 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.

In the present embodiment, one type of resin (Q) may be used alone, or two or more types may be used in combination.

[Compatible agent (R)]
The resin composition according to the present embodiment is selected from the group consisting of a cyclic olefin copolymer (P) and a polyphenylene ether, a polyimide resin, a polyurethane, a polyether ether ketone, a polybutylene terephthalate, a liquid crystal polymer, a maleimide resin, and a polybutadiene resin. From the viewpoint of improving the compatibility with one or more kinds of resins (Q), it is preferable to further contain the compatibilizer (R).
In the present embodiment, the compatibilizer (R) is a group consisting of a cyclic olefin copolymer (P), polyphenylene ether, polyimide resin, polyurethane, polyetheretherketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. It is a compound that is compatible with one or more kinds of resins (Q) selected from the above.
Examples of the compatibilizer (R) include modified polyolefins, modified elastomers, compounds having polar groups in the molecule and unsaturated carbon bonds capable of contributing to the polymerization reaction.

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 crosslinked 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. Oligomers, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, chlorosulfated polyethylene, ethylene vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, chlorination Examples thereof include polyethylene, a styrene-ethylene-butylene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer. 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 crosslinked 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 (R) 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 crosslinked 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 crosslinked product.

Examples of compounds that can be used as the compatibilizer (R) are listed above, but these can be used alone or in combination of two or more.
The content of the compatibilizer (R) is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, when the cyclic olefin copolymer (P) in the resin composition is 100 parts by mass. is there.

[Additive]
Various additives may be added to the resin composition according to the present embodiment, depending on the purpose. The amount of the additive added is appropriately selected according to the application within a range that does not impair the object of the present invention.
Examples of the above additives include heat-resistant stabilizers, weather-resistant stabilizers, radiation-resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction-wear improvers, flame retardants, foaming agents, antistatic agents, colorants, and anti-corrosion agents. One or more additives selected from the group consisting of frosting agents, antiblocking agents, impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbers, metal inactivating agents and hardening accelerators. ..

Examples of the heat-resistant stabilizer include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester subphosphorus. Acids, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) pentaerythritol Phenyl heat stabilizers such as diphosphite; lactone heat stabilizers such as reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3, 3', 3 ", 5,5', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-cresol, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Such as hindered phenol-based heat-stabilizing agent; sulfur-based heat-stabilizing agent; amine-based heat-resistant stabilizer and the like. Further, these can be used alone or in combination of two or more. Among them, phos. Fight-based heat-stabilizing agents and hindered phenol-based heat-resistant stabilizers are preferable.

As the weather-resistant stabilizer, one or more compounds selected from light stabilizers, antioxidants, ultraviolet absorbers and the like can be used.

Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. 6-Tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinateimide, 1-[(3,5-ditertiary butyl-4-hydroxyphenyl) ) Propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditetrabutyl-4-hydroxyphenyl) propionate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (1,2,2,6,6, -pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6- Tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl)- 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2-{tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyl Oxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2-{tris (1,2,2,6,6- Pentamethyl-4-piperidyloxycarbonyloxy) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis { N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazine-2-yl] -1,5,8,12-tetraazadodecane, 1-( 2-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-third octylamino-4,6-dichloro-s-triazine / N, N'- Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromo Ethan condensate, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxyl, bis (2,2,6,6-tetramethyl-N-oxylpiperidin) sebacate, tetrakis (2,2) 6,6-Tetramethyl-N-oxypiperidyl) butane-1,2,3,4-tetracarboxylate, 3,9-bis (1,1-dimethyl-2- (tris (2,2,6,6)) -Tetramethyl-N-oxylpiperidyl-4-oxycarbonyl) butylcarbonyloxy) ethyl) 2,4,6,10-tetraoxalospyro [5.5] undecane, 1,6-bis (2,2,6) 6-Tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6- Tertiary octylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine weight Condensate, 2,2,6,6-tetramethyl-4-piperidinol, tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl- Condensate of 4-piperidinol with 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol with tridecyl alcohol and 1,2,3,4-butane Condensate with tetracarboxylic acid, condensate with 1,2,2,6,6-pentamethyl-4-piperidinol and 1,2,3,4-butanetetracarboxylic acid, 1- [2- [3-( 3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-3,5-di-t-butyl-4-hydroxyphenyl] propionyloxy] -2,2,6 , 6-Tetramethylpiperidine (eg, Sanol LS-2626, manufactured by Sankyo), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis- ( 1,2,2,6,6-pentamethyl-4-piperidyl) (eg, Tinuvin144, manufactured by BASF), bis (2,2', 6,6'-tetramethyl-4-piperidyl) sevacay (For example, TINUVIN770, manufactured by BASF), Poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2) 6,6-Tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] (for example, CHIMASSORB944, manufactured by BASF) and the like can be mentioned.

Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, thioether-based antioxidants, and the like.

Examples of the phenolic antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 2,4-di-t-. Amil-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like, acrylates described in JP-A-63-179953 and JP-A-1-168643. Phenol compounds; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (6-t-butyl-m-cresol), 4,4' -Thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-t-butyl-4)) -Hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl- 4-Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene- 3- (3', 5'-di-t-butyl-4'-hydroxyphenylpropionate) methane [ie, pentaerythrimethyl-tetrakis (3- (3,5-di-t-butyl-4-hydroxy) Phenylpropionate)], triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), alkyl-substituted phenolic compounds such as tocophenol; 6- (4-hydroxy-3) , 5-Di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bisoctylthio- 1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6- Triazine group-containing phenolic compound such as bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine Things; etc. Among these, acrylate-based phenolic compounds and alkyl-substituted phenolic compounds are preferable, and alkyl-substituted phenolic compounds are particularly preferable.

Examples of the phosphorus-based antioxidant include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-). Di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) ) Octylphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- Monophosphite compounds such as 9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis ( 3-Methyl-6-t-butylphenyl-di-tridecylphosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene -Bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4) -Di-t-butylphenyl) -4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis (isodecylphosphite), cyclic neopentanetetraylbis (nonylphenylphosphite), cyclic neo Pentantetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis (2,6-di) -T-Butylphenylphosphite) and other diphosphite compounds and the like can be mentioned. Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.

Examples of the sulfur-based antioxidant include dilauryl-3,3-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3-thiodipropionate, and laurylstearyl-3. , 3-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane and the like can be mentioned.

Examples of the thioether-based antioxidant include tetrakis {methylene-3- (laurylthio) propionate} methane and bis [methyl-4- {3-n-alkyl (C12 or C14) thiopropioniodyl} -5-t. -Butylphenyl] Sulfide, ditridecyl-3,3'-thiodipropionate and the like.

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, acrylate-based ultraviolet absorbers, metal complex salt-based ultraviolet absorbers, and the like.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, and 2-hydroxy-4. -Octyloxybenzophenone, 4-dodecaloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'- Examples thereof include dimethoxybenzophenone.

Examples of the salicylic acid-based ultraviolet absorber include phenylsultylate, 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, and 2,4-di-t-butylphenyl-3,5-. Examples thereof include di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) 2H-benzotriazole and 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5. Chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-) Hydroxyphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-amyl-) 2-Hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octylphenyl) -2H-benzotriazole, 2 -(2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- [(2H-benzotriazole-2-yl) phenol]] and the like.

Examples of the acrylate-based ultraviolet absorber include ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate and the like.

As the metal complex salt-based ultraviolet absorber, a complex salt of nickel or cobalt is usually used. Specifically, nickel [2,2'thiobis (4-t-octyl) phenolate] normal butylamine, nickel dibutyl dithiocarbamate, nickel bis [o-ethyl-3,5- (di-t-butyl-4-)). Hydroxybenzyl)] phosphate, cobalt dicyclohexyldithiophosphate, [1-phenyl, 3-methyl, 4-decanonyl, pyrazolate (5) 2] nickel and the like.

Examples of the radiation resistant agent include rosin, rosin derivatives (for example, modified rosins such as hydride rosin, disproportionated rosin, and polymerized rosin, and modified rosin esters thereof), terpene resins, terpene phenol resins, and aromatic modifications. Examples thereof include terpene resin, hydride terpene resin, aliphatic petroleum resin, aromatic petroleum resin, copolymerized petroleum resin, alicyclic petroleum resin, hydride petroleum resin, alkylphenol resin and the like.

Examples of the plasticizer include tricresyl phosphate, trixysilyl phoslate, triphenyl phoslate, triethylphenyl phoslate, diphenyl cresyl phosphate, monophenyl dicrezyl phoslate, and dicrezyl monoxylenyl phoslate. Phthalate triester-based plasticizers such as arylalkyl phosphate, diphenylmonoxylenyl phosphate, morphophosphate, trioctyl phosphate, tris (isopropylphenyl) phosphate; dimethyl phthalate, diethyl phthalate, phthalate. Phthalate-based plasticizers such as dibutyl, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, octyldecyl phthalate, butylbenzyl phthalate; butyl oleate, glycerin mono Fatty monobasic acid ester-based plasticizers such as oleic acid ester; dibutyl adipate, di-n-fatty acid dibasic acid ester-based plasticizer; dihydric alcohol ester-based plasticizer; oxyacid ester-based plasticizer, etc. Be done.

Examples of the lubricant include waxes, oils, caprins, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid and other higher fatty acids or metal salts thereof, that is, lithium salts. Fatty acids such as calcium salt, sodium salt, magnesium salt, potassium salt, palmitic acid, cetyl alcohol, stearyl alcohol, caproic acid amide, capric acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid Examples thereof include aliphatic amides such as acid amides and stearic acid amides, esters of fatty acids and alcohols, fluoroalkylcarboxylic acids or metal salts thereof, and fluorine compounds such as fluoroalkylsulfonic acid metal salts.
Examples of the above waxes include montan wax, peat wax, ozokelite selecine wax, mineral wax such as petroleum wax, polyolefin wax such as polyethylene wax and polypropylene wax, Fisher-Tropsch wax, chemically modified hydrocarbon wax, and substituted amide. Examples include synthetic wax such as wax, plant wax, animal wax and the like.
Examples of the above-mentioned oils include natural and synthetic oils such as aromatic oils, naphthenic oils, paraffinic mineral oils, vegetable oils and silicon oils. As the silicone oil, dimethylpolysiloxane having a viscosity of 10 to 5000 cSt, preferably 500 cSt can be used.

Examples of the release agent include lower (C1 to 4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4 to 30) (hardened paraffin oil, etc.), and glycol esters of fatty acids. Liquid paraffin and the like can be mentioned.

Examples of the nucleating agent include sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate and [phosphate-2,2'-methylenebis (4,6-di-t-butyl). Phenyl)] dihydrooxyaluminum, bis [phosphate-2,2'-methylenebis (4,6-di-t-butylphenyl)] hydrooxyaluminum, tris [phosphate-2,2'-methylenebis (4,6) -Di-t-Butylphenyl)] Aluminum, sodium-bis (4-t-butylphenyl) phosphate, metal benzoates such as sodium benzoate, aluminum pt-butyl benzoate, 1,3: 2,4 -Bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (O-methylbenziliden) sorbitol, 1,3: 2,4-bis (O-ethylbenzylidene) sorbitol, 1,3-O-3 , 4-Dimethylbenzylidene-2,4-O-Bendylidene sorbitol, 1,3-O-Benzilidene-2,4-O-3,4-Dimethylbenzylidene sorbitol, 1,3: 2,4-Bis (O-3) , 4-Dimethylbenzylene) sorbitol, 1,3-O-p-chlorobenzylidene-2,4-O-3,4-dimethylbenzylene sorbitol, 1,3-O-3,4-dimethylbenzylene-2,4- Examples thereof include Op-chlorobenzylene sorbitol, 1,3: 2,4-bis (Opp-chlorobenzylidene) sorbitol, and mixtures thereof.

Examples of the friction and wear improving agent include resin fillers such as ultra-high molecular weight polyethylene fillers, PTFE fillers and polyimide fillers, and inorganic fillers such as boron nitride fillers and aluminum nitride fillers.

As the flame retardant, for example, a halogen-based flame retardant, a phosphorus-based flame retardant, a nitrogen-containing flame retardant, and an antimony-based flame retardant can be used.
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, dileph alder reaction adduct 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-halogen-based phosphoric acid ester flame-retardant such as aromatic phosphoric acid ester, etc .; Examples thereof include aluminum phosphite-based flame retardant such as aluminum dimethylphosphinate and aluminum diethylphosphinate.
Examples of the nitrogen-containing flame retardant include melamine cyanurate, isocyanuric acid, tris (2-hydroxyethyl) isocyanurate, triallyl isocyanurate, tris (2,3-epoxypropyl) isocyanurate, guanidine hydrochloride, guanidine nitrate, and phosphoric acid. Guanidin, guanidine sulfate, guanidine sulfamate, guanidine tetraborate, guanidine carbonate, guanylurea phosphate, guanylurea sulfate, melamine, melamine, melamine, melem, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polyline Examples thereof include melamine acid, melamine, melem, and melamine sulfate.
Examples of the antimony-based flame retardant include antimony oxide, antimony trioxide, antimony pentoxide, antimony tetroxide, and sodium antimonate.

Examples of the antistatic agent and antifogging agent include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants.

Examples of the cationic surfactant include tetraalkylammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride.

Examples of the anionic surfactant include sodium decane sulfonate, sodium indecane sulfonate, sodium dodecane sulfonate, sodium tridencan sulfonate, sodium tetradecane sulfonate, sodium pentadencan sulfonate, and sodium hexadecane sulfonate. , Sodium heptadencan sulfonate, sodium octadecane sulfonate, sodium nonadecan sulfonate, sodium heeicosan sulfonate, potassium decane sulfonate, potassium undecane sulfonate, potassium dodecane sulfonate, potassium tridecane sulfonate, tetradecane sulfonic acid Alkyl sulfonates such as potassium, potassium pentadecane sulfonate, potassium hexadecane sulfonate, potassium heptadecane sulfonate, potassium octadecane sulfonate, potassium nonadecan sulfonate, potassium heeikosandeca sulfonate, sodium decylbenzene sulfonate, un Sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, sodium pentadecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, sodium heptadecylbenzenesulfonate, octadecylbenzenesulfone Examples thereof include alkylbenzene sulfonates such as sodium acid acid and alkyl phosphates.

Examples of the amphoteric surfactant include betaine compounds such as lauryl betaine, stearyl betaine, laurylamide propyl betaine and stearylamide propyl betaine, dimethylamine oxide compounds such as lauryldimethylamine oxide and stearyldimethylamine oxide, and N-stearyl-. Examples thereof include alanine compounds such as α-alaninate and N-lauryl-α-alaninate.

Examples of the nonionic surfactant include laurate monoglyceride, palmitate monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride, caprylic acid monoglyceride, coconut fatty acid monoglyceride, laurate diglyceride, palmitate diglyceride, and stearic acid diglyceride. , Oleate diglyceride, behenic acid diglyceride, capric acid diglyceride, palm fatty acid diglyceride, laurate triglyceride, palmitate triglyceride, stearic acid triglyceride, oleic acid triglyceride, behenic acid triglyceride, caprylate triglyceride, palm fatty acid triglyceride, pentaeryth , Pentaerythritol monostearate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetralaurate and other pentaerythritol fatty acid esters, sorbitol monolaurate, sorbitol monostearate. Rate, fatty acid ester of sorbitol Polyhydric alcohol fatty acid ester such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, etc., laurate diethanolamide, stearic acid Examples thereof include diethanolamides such as diethanolamide and coconut fatty acid diethanolamide.

As the colorant, for example, various natural and synthetic dyes and various inorganic and organic pigments can be arbitrarily used.

Examples of the antiblocking agent include fine particle inorganic compounds such as silica, alumina, alumina silicate and diatomaceous earth, and fine particle organic compounds such as polyethylene, cross-linked polyethylene, polymethyl methacrylate and cross-linked polymethyl methacrylate.

As the impact resistant agent, for example, various agents such as a (meth) acrylic acid ester-based impact resistant agent having a core-shell type structure can be used.

Examples of the surface wetting improving agent include silane coupling agents such as vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Be done.

Examples of the filler include an inorganic filler and an organic filler.
Examples of the inorganic filler include silica, diatomaceous soil, alumina, titanium oxide, magnesium oxide, pebbles powder, pebbles balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, and potassium titanate. , Barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide and the like. These may be used alone or in combination of two or more.

Examples of the organic filler include starch and its derivatives, cellulose and its derivatives, pulp and its derivatives, paper and its derivatives, flour, okara, bran, coconut shells, coffee bran, proteins, phthalates, and fats. Examples thereof include group polybasic acid-based, glycerin-based, citric acid-based, glycol-based, and olefin-based low molecular weight compounds, polyethylene terephthalate fiber, polyethylene naphthalate fiber, and aramid fiber.

Examples of the hydrochloric acid absorber include higher fatty acid metal salts. Specifically, sodium stearate, magnesium stearate, calcium stearate, zinc stearate, lithium stearate, barium stearate, aluminum stearate, sodium 12-hydroxystearate, calcium 12-hydroxystearate, 12-hydroxystearic acid. There are magnesium, zinc 12-hydroxystearate and the like. In addition, epoxy compounds such as octyl epoxidized stearate and epoxidized soybean oil; inorganic compounds such as magnesium hydroxide, calcium hydroxide and hydrotalnite can be mentioned.

Examples of the metal inactivating agent include N, N'-diphenyloxamide, N-salicyral-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis ( 3,5-Di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazol, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacylbis Examples thereof include phenylhydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide and the like.

[Method for preparing resin composition]
The method for preparing the resin composition according to the present embodiment is from the cyclic olefin copolymer (P), polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. It can be prepared by mixing one or more kinds of resins (Q) selected from the above group, a compatibilizer (R) if necessary, and various additives. As a mixing method, a method of melt-blending with an extruder or the like, or a suitable solvent such as saturated hydrocarbons such as heptane, hexane, decane and cyclohexane; dissolved in aromatic hydrocarbons such as toluene, benzene and xylene, etc. A solution blending method or the like performed by dispersing can be adopted.

[varnish]
The resin composition according to this embodiment can be made into a varnish by mixing with a solvent.
The solvent for preparing the varnish includes a group consisting of a cyclic olefin copolymer (P) and a polyphenylene ether, a polyimide resin, a polyurethane, a polyether ether ketone, a polybutylene terephthalate, a liquid crystal polymer, a maleimide resin, and a polybutadiene resin. It is not particularly limited as long as it does not impair the solubility or affinity for one or more selected resins (Q).
Preferred solvents are, for example, saturated hydrocarbons such as heptane, hexane, octane, decane; lipocyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene; aromatics such as toluene, benzene, xylene, mesitylene and pseudocumene. Group hydrocarbons; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol; ketone solvents such as acetone, methylisobutylketone, methylethylketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone; methyl Cellsolves such as cellsolve and ethyl cellsolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate; halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene are used. .. Preferably, heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene, methylethylketone and cyclohexanone are used. These solvents can be used alone or in admixture of two or more in any proportion.

In the present embodiment, the method for preparing the varnish may be any method, but usually includes a step of mixing the 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.
The reaction solution obtained when the cyclic olefin copolymer (P) was obtained was used as it was as a solvent, and polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and A varnish may be prepared by dissolving one or more resins (Q) selected from the group consisting of polybutadiene resins. Further, after purifying the cyclic olefin copolymer (P), it is separately selected from the group consisting of polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin1. A varnish may be prepared by adding a seed or two or more kinds of resin (Q) and a solvent.

[Crosslink (L)]
The crosslinked body (L) is a crosslinked product of the resin composition according to the present embodiment, and is a cyclic olefin copolymer (P) in the above-mentioned resin composition and polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, and the like. It is obtained by cross-linking one or more resins (Q) selected from the group consisting of polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. The method for cross-linking the cyclic olefin copolymer (P) and the resin (Q) is not particularly limited, but any cross-linking agent such as a radical polymerization initiator or a hydrosilyl group-containing compound, an electron beam or other radiation may be used. Examples thereof include a method of cross-linking while molding into the shape of the above, or after molding.

For cross-linking with a radical polymerization initiator, the usual cross-linking method with a radical polymerization initiator applied for polyolefin can be applied as it is. That is, a radical polymerization initiator such as dicumyl peroxide is added to the resin composition, and the resin composition is heated and crosslinked. Although the blending ratio of the radical polymerization initiator is not particularly limited, it is usually 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.05 to 10 parts by mass per 100 parts by mass of the cyclic olefin copolymer (P). Is 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 crosslinked body (L) is improved, and when it is more than the above lower limit value, the heat resistance and mechanical properties of the crosslinked body (L) are improved. Can be made to.

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). Dialkyl peroxides such as oxy) 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) valerate, ethyl-3,3-bis (t-butylperoxy) butyrate, 3,3,6,6,9,9-hexamethyl-1, Peroxyketals such as 2,4,5-tetraoxycyclononane; peroxyesters such as bis (t-butylperoxy) isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate; t- Butyl hydroperoxides, t-hexyl hydroperoxides, cumin hydroperoxides, 1,1,3,3-tetramethylbutylhydroperoxides, diisopropylbenzene hydroperoxides, p-menthan hydroperoxides and other hydroperoxides. Bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepan and the like.

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 anthracene, 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.

The temperature at which the resin composition is crosslinked with the radical polymerization initiator is usually 100 to 300 ° C., preferably 120 to 250 ° C., more preferably 120 to 220 ° C., and the temperature is changed stepwise to carry out the crosslinking. May be good. When it is at least the above lower limit value, the cross-linking can be sufficiently advanced. Further, when it is not more than the above upper limit value, coloring of the obtained crosslinked product can be suppressed and the process can be simplified. As a reference, polybutadiene, which is a typical double bond-containing polymer, cannot be crosslinked under the above conditions in general, and requires a crosslinking condition at a high temperature such as 300 ° C.

The resin composition according to the present embodiment can also be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule. Cross-linking using a hydrosilyl group-containing compound can be performed, for example, according to the method described in JP-A-2015-193680. Details are omitted here.

The method of cross-linking 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. ..

In any of the methods using a radical polymerization initiator, a hydrosilyl group-containing compound, and the like, and the method of cross-linking using radiation, cross-linking can be performed in combination with a cross-linking aid.

The cross-linking aid is not particularly limited, but for example, oximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylpropantrimethacrylate, cyclohexyl. Alacrylates or methacrylates such as methacrylate, acrylic acid / zinc oxide mixture, allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; hexamethylene diallyl nadiimide, diallyl itacone, diallyl phthalate, diallyl isophthalate, diallyl. Allyl compounds such as monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate; maleimide such as N, N'-m-phenylene bismaleimide, N, N'-(4,4'-methylenediphenylene) dimaleimide. Examples of compounds include cyclic non-conjugated diene such as vinyl norbornene, etilidennorbornene, and dicyclopentadiene. These cross-linking aids may be used alone or in combination.

The cross-linking reaction can be carried out in a molten state of a mixture of the resin composition and the above-mentioned radical polymerization initiator or a compound such as a hydrosilyl group-containing compound, or a solution in which the mixture is dissolved or dispersed in a solvent. It can be carried out in a state, or the solvent can be volatilized from a solution state dissolved in a solvent to form an arbitrary shape such as a film or a coating, and then the cross-linking reaction can be further advanced.

When the reaction is carried out in a molten state, the 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 cross-linking 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 cross-linking reaction is carried out using an electron beam or other radiation or UV, the reaction can be carried out after shaping by any method.

[Film or sheet]
The crosslinked body of the resin composition according to this embodiment can be molded into a film or a sheet and used for various purposes. Various known methods can be applied as a method for forming a film or a sheet using the 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 resin composition to crosslink the resin composition. 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 film or a sheet by melt-molding the resin composition according to the present embodiment can also be mentioned.

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

[Multilayer molded product or multilayer laminated film]
The resin composition according to this embodiment may be formed on the surface layer of various multilayer molded products or multilayer laminated films. At this time, the resin layer formed by the resin composition is preferably 100 μm or less.
Examples of various multilayer molded bodies or multilayer laminated films include multilayer molded bodies for optical lenses in which the resin composition according to the present embodiment is formed on the surface of a resin optical lens, and the surface of a resin film such as a PET film or PE film. Examples thereof include a multilayer gas barrier film on which the resin composition according to the present embodiment is formed in order to impart gas barrier properties.

[Interlayer insulation film]
The resin composition according to the present embodiment can also be used as an interlayer insulating film for forming an insulating layer in a build-up layer in a multilayer circuit board in which a plurality of layers of electronic circuits are stacked. That is, the resin composition according to this embodiment can be used for a multilayer circuit board.

[Prepreg]
Further, the prepreg according to the present embodiment is formed by combining the resin composition according to 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 a heating furnace 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.

Inorganic and / or organic fibers can be used as the fibers constituting the sheet-shaped fiber base material according to the present embodiment, and are not particularly limited, but for example, PET (polyethylene terephthalate) fibers, aramid fibers, and ultra-high molecular weight polyethylenes. Organic fibers such as fibers, polyamide (nylon) fibers and liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers and silica fibers. ; Etc. 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. Examples of the glass fiber include E glass, NE glass, S glass, D glass, H glass, T glass and the like.
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 and mechanical strength of the obtained laminate are highly balanced and 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 laminate obtained by curing are sufficiently exhibited and are suitable.

[Circuit board]
As described above, the resin composition according to the present embodiment is excellent in dielectric properties, heat resistance, mechanical properties, etc., and therefore can be suitably used for a circuit board.
A generally known method can be adopted as a method for manufacturing a circuit board, and the method is not particularly limited. For example, a 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. Next, the conductor layer is laminated on the obtained electrically insulating layer by a known method to prepare a laminated body. After that, a circuit board can be obtained by processing the conductor layer in the laminated body by circuit processing or the like.

As the metal to be the conductor layer, metals such as copper, aluminum, nickel, gold, silver, and stainless steel can be used. Examples of the method for forming the conductor layer include a method in which the metals are made into a foil or the like and heat-sealed onto the electrically insulating layer, and a method in which the metals are made into a foil or the like and bonded onto the electrically insulating layer using an adhesive. Alternatively, a method of forming a conductor layer made of the metal on the electrically insulating layer by a method such as sputtering, vapor deposition, or plating can be mentioned. The form of the circuit board may be either a single-sided plate or a double-sided plate.

Such a circuit 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.

[Use]
The resin composition and the crosslinked body (L) according to the present embodiment are particularly excellent in dielectric properties and dielectric properties over time, and are also excellent in solvent resistance, heat resistance, transparency, mechanical properties and the like. Therefore, it can be suitably used for high frequency applications such as high frequency circuit boards, interlayer insulating films, and laminates.

（上記一般式（Ｉ）において、Ｒ ^３００ 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。）
２．１．に記載の樹脂組成物において、
前記樹脂（Ｑ）がポリフェニレンエーテルを含む樹脂組成物。
３．１.または２.に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
下記一般式（Ｖ）で表される繰り返し単位、下記一般式（ＶＩ）で表される繰り返し単位および下記一般式（ＶＩＩ）で表される繰り返し単位からなる群から選ばれる少なくとも１種の非共役ジエン系オレフィン由来の繰り返し単位（ｃ）の含有量が０．０５モル％以下である樹脂組成物。

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

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

（上記一般式（ＶＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ ^６１ 〜Ｒ ^７６ ならびにＲ ^ａ１ およびＲ ^ｂ１ は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ ^１０４ は水素原子または炭素原子数１〜１０のアルキル基であり、ｔは０〜１０の正の整数であり、Ｒ ^７５ およびＲ ^７６ は、互いに結合して単環または多環を形成していてもよい。）
４．１．乃至３．のいずれか一項に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中の前記α−オレフィン由来の繰り返し単位（ａ）が、前記一般式（Ｉ）においてＲ ^３００ が炭素原子数２以上１０以下の直鎖状の炭化水素基である繰り返し単位を含む樹脂組成物。
５．１．乃至４．のいずれか一項に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中の前記環状オレフィン由来の繰り返し単位（ｂ）が、ビシクロ［２．２．１］−２−ヘプテンおよびテトラシクロ［４．４．０．１ ^２，５ ．１ ^７，１０ ］−３−ドデセンから選ばれる少なくとも一種の化合物に由来する繰り返し単位である樹脂組成物。
６．１．乃至５．のいずれか一項に記載の樹脂組成物において、
前記環状オレフィン共重合体（Ｐ）中に含まれる繰り返し単位の合計を１００モル％としたとき、
前記環状オレフィン由来の繰り返し単位（ｂ）の含有量が１０モル％以上９０モル％以下である樹脂組成物。
７．１．乃至６．のいずれか一項に記載の樹脂組成物において、
耐熱安定剤、耐候安定剤、耐放射線剤、可塑剤、滑剤、離型剤、核剤、摩擦磨耗性向上剤、難燃剤、発泡剤、帯電防止剤、着色剤、防曇剤、アンチブロッキング剤、耐衝撃剤、表面ぬれ改善剤、充填材、塩酸吸収剤、金属不活性化剤および硬化促進剤からなる群から選択される一種または二種以上の添加剤をさらに含む樹脂組成物。
８．１．乃至７．のいずれか一項に記載の樹脂組成物と溶媒を含有するワニス。
９．１．乃至７．のいずれか一項に記載の樹脂組成物の架橋体。
１０．９．に記載の架橋体を含むフィルムまたはシート。
１１．１０．に記載のフィルムまたはシートを基材に積層した積層体。
１２．９．に記載の架橋体を含む電気絶縁層と、前記電気絶縁層上に設けられた導体層とを含む回路基板。
１３．１２．に記載の回路基板を備えた電子機器。
１４．１．乃至７．のいずれか一項に記載の樹脂組成物とシート状繊維基材とを含むプリプレグ。
１５．１．乃至７．のいずれか一項に記載の樹脂組成物が表層に厚み１００μｍ以下で形成された多層成形体または多層積層フィルム。
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, an example of the reference form will be added.
1. 1. One or more selected from the group consisting of cyclic olefin copolymer (P) and polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. A resin composition containing a resin (Q).
The mass ratio ((Q) / (P)) of the content of the resin (Q) to the content of the cyclic olefin copolymer (P) in the resin composition is 0.1 or more and 5 or less.
The cyclic olefin copolymer (P) is
The repeating unit (a) derived from at least one α-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 resin composition containing the derived repeating unit (b).

(In the above general formula (I), R ³⁰⁰ represents 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 the same as 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. .)
2.1. In the resin composition described in
A resin composition in which the resin (Q) contains polyphenylene ether.
In the resin composition according to 3.1 or 2.
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
At least one non-conjugated unit selected from the group consisting of a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating unit represented by the following general formula (VII). A resin composition in which the content of the repeating unit (c) derived from a diene-based olefin is 0.05 mol% or less.

(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.)
4.1. To 3. In the resin composition according to any one of
The repeating unit (a) derived from the α-olefin in the cyclic olefin copolymer (P) is a linear hydrocarbon group having R ³⁰⁰ having 2 or more and 10 or less carbon atoms in the general formula (I). A resin composition containing a repeating unit.
5.1. To 4. In the resin composition according to any one of
The repeating unit (b) derived from the cyclic olefin in the cyclic olefin copolymer (P) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . 1 ^{7,10] -3-resin} composition is a repeating unit derived from at least one compound selected from dodecene.
6.1. To 5. In the resin composition according to any one of
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
A resin composition in which the content of the repeating unit (b) derived from the cyclic olefin is 10 mol% or more and 90 mol% or less.
7.1. To 6. In the resin composition according to any one of
Heat-resistant stabilizer, weather-resistant stabilizer, radiation-resistant agent, plasticizer, lubricant, mold release agent, nucleating agent, friction abrasion improver, flame retardant, foaming agent, antistatic agent, colorant, antifogging agent, anti-blocking agent A resin composition further comprising one or more additives selected from the group consisting of impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbents, metal deactivators and curing accelerators.
8.1. To 7. A varnish containing the resin composition according to any one of the above and a solvent.
9.1. To 7. The crosslinked product of the resin composition according to any one of the above.
10.9. A film or sheet containing the crosslinked product according to.
11.10. A laminate obtained by laminating the film or sheet described in 1. on a base material.
12.9. A circuit board including an electrically insulating layer including the crosslinked body according to the above, and a conductor layer provided on the electrically insulating layer.
13.12. An electronic device equipped with the circuit board described in.
14.1. To 7. A prepreg containing the resin composition according to any one of the above and a sheet-like fiber base material.
15.1. To 7. A multilayer molded product or a multilayer laminated film in which the resin composition according to any one of the above items is formed on the surface layer having a thickness of 100 μm or less.

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 following raw materials were used in the experiment.

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

(Cyclic olefin copolymer (P))
Cyclic olefin copolymer (P-1): 1-octene (hereinafter, also referred to as C8) and tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene (hereinafter, also referred to as TD) copolymer (C8 / TD = 34/66 (molar ratio), Tg: 246 ° C.)
Cyclic olefin copolymer (P-2): 1-hexene (hereinafter, also referred to as C6) and tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] A copolymer composed of -3-dodecene (C6 / TD = 65/35 (molar ratio), Tg: 188 ° C.)
Cyclic olefin copolymer (P-3): Copolymer composed of ethylene and bicyclo [2.2.1] -2-heptene (Product name: Topas 6013S-04, manufactured by Polyplastics, Tg: 138 ° C.)

(Resin (Q))
Resin (Q-1): Modified polyphenylene ether synthesized according to Synthesis Example 3 below Resin (Q-2): Modified polyphenylene ether (SABIC Innovative Plastics) in which the terminal hydroxyl group of the polyphenylene ether of the above formula (7) is modified with a methacrylic group. SA9000 made by the company)

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

(Weather resistant stabilizer)
Weather Stabilizer 1: Chimasorb 944 (manufactured by BASF)
Weather Stabilizer 2: Irganox 1010 (manufactured by BASF)

(Filler)
Filler 1: Crushed silica (manufactured by Ryumori Co., AS-1)

(Glass cloth)
Glass cloth 1: 1031NT S640 (manufactured by Arisawa Mfg. Co., Ltd.)

(Crosslinking agent)
Crosslinking agent 1: Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D)

(Crosslinking aid)
Crosslinking aid 1: Divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Crosslinking aid 2: Polybutadiene (manufactured by Nippon Soda)

(Other)
MAO (manufactured by Nippon Aluminum Alkyls, Inc.)
Tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-Dodecene (manufactured by Mitsui Chemicals, Inc.)

[Synthesis Example 1: Synthesis of Cyclic Olefin Copolymer (P-1)]
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 . 1 ^7,10] -3-dodecene (TD) 20.0 mL, 1-octene 5.5mL as α- olefins, methylaluminoxane (MAO) was added 10mmol of aluminum atom basis. 0.010 mmol of the transition metal compound (1) dissolved in toluene was added to initiate polymerization. After continuing the polymerization at 25 ° C. for 15 minutes, the polymerization was stopped by adding isobutyl alcohol. The reaction product was put into a mixed solvent of acetone / methanol (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-octene copolymer. The monomer composition in the polymer determined by NMR was 66 mol% of TD, 34 mol% of 1-octene, and the glass transition temperature measured by DSC was 246 ° C.
Here, the NMR analysis method followed the method described in Macromolecules 2016, 49, 59-70.

[Synthesis Example 2: Synthesis of Cyclic Olefin Copolymer (P-2)]
A TD / 1-hexene copolymer was synthesized in the same manner as in Synthesis Example 1 except that the α-olefin was 1-hexene 28.2 mL. The monomer composition in the polymer determined by NMR was 35 mol% of TD, 65 mol% of 1-hexene, and the glass transition temperature measured by DSC was 188 ° C.

[Synthesis Example 3: Synthesis of Resin (Q-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.
To a glass reactor charged with 200 g of toluene, 100 g of polyphenylene ether oligomer (SA90 manufactured by SABIC), 15 g of chloromethylstyrene, and 0.6 g of tetrabutylammonium bromide were added and heated to 75 ° C. with stirring to dissolve them. 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 4: Synthesis of Maleic anhydride-Modified Polystyrene / Polybutadiene / Polystyrene Triblock Copolymer (Compatible Agent (R-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.

[Example 1]
(Preparation of resin composition varnish)
Each raw material was dissolved in toluene at the compounding ratio shown in Table 1 (the numerical values in the table indicate parts by mass) to obtain a curable resin composition varnish.

(Preparation of resin composition film)
The obtained resin composition-dissolved varnish was applied to a PET film that had been released from the mold at a rate of 10 mm / sec, and then dried in a blower dryer under a nitrogen stream set at 110 ° C. for 10 minutes. Then, the temperature was raised to 180 ° C. and heated for 2 hours to obtain a film made of a crosslinked product.
The obtained film was peeled off from the PET film and evaluated by the method shown below. The results obtained are shown in Table 1.

(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 resin composition was evaluated according to the following criteria.
◯: Storage elastic modulus (E') at 250 ° C. is 1 × 10 ⁶ Pa or more ×: Storage elastic modulus (E') at 250 ° C. is less than 1 × 10 ⁶ Pa Here, storage elastic modulus (E') is 1 If it is × 10 ⁶ Pa or more, it has been confirmed in the solder heat resistance test that no appearance abnormality occurs.

(2) Dielectric characteristics The dielectric loss tangent of the film at 12 GHz was measured by the cylindrical cavity resonator method. Specifically, a synthesized sweeper (8340B manufactured by YHP) and a test set (8515A) were used to evaluate the dielectric loss tangent of the film at 12 GHz.
◯: Dissipation factor is less than 0.0020 ×: Dissipation factor is 0.0020 or more

(3) Breaking strength The breaking strength was measured by pulling from both ends of the test piece at a tensile speed of 30 mm / min using a universal material testing machine (type 201-5, manufactured by Intesco). For the measurement, a test piece punched into a dumbbell shape having a length of 50 mm and a width of 5 mm from the press films obtained in each Example and Comparative Example was used. The breaking strength was evaluated according to the following criteria.
◯: Breaking strength is 50 MPa or more ×: Breaking strength is less than 50 MPa

[Examples 2 to 5, Comparative Examples 1 and 2]
Films were prepared and evaluated in the same manner as in Example 1 except that the blending ratio of each component was changed to the blending ratio shown in Table 1.
The results obtained are shown in Table 1.

[Example 6]
(Making prepreg 1)
The glass cloth 1 was impregnated with the resin composition varnish obtained in Example 2 and dried in a blower dryer at 120 ° C. for 10 minutes to prepare a prepreg 1 having a thickness of 0.1 mm.

(Preparation of laminated body 1)
Eight prepregs 1 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 a laminated body 1. The obtained laminate 1 was evaluated by the method shown below. The results obtained are shown in Table 2.

(1) Solder Heat Resistance The laminated body 1 was immersed in a solder bath at 288 ° C. for 20 seconds, and then the state of the laminated body 1 was observed. The solder heat resistance of the laminate 1 was evaluated based on the following criteria.
◯: Both deformation and swelling did not occur ×: At least one of deformation and swelling occurred

(2) Dielectric characteristics 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) was used to measure the dielectric loss tangent of the laminate at 12 GHz.
◯: Dissipation factor is less than 0.0025 ×: Dissipation factor is 0.0025 or more

(3) Thermal stability The obtained laminate was allowed to stand in an oven at a temperature of 200 ° C. and taken out after 100 hours. The thermal stability was evaluated from the state of the taken-out laminate.
The thermal stability of the laminate was evaluated according to the following criteria.
◯: No abnormality in the laminate ×: Cracks in the laminate

[Example 7 and Comparative Example 3]
Prepregs 2 and 3 were prepared in the same manner as in Example 6 except that the resin composition varnish was changed to the resin composition varnish described in Example 4 and Comparative Example 2, respectively, and further in the same manner as in Example 6. Laminates 2 and 3 were prepared and evaluated.
The results obtained are shown in Table 2.

Claims (14)

One or more selected from the group consisting of cyclic olefin copolymer (P) and polyphenylene ether, polyimide resin, polyurethane, polyether ether ketone, polybutylene terephthalate, liquid crystal polymer, maleimide resin, and polybutadiene resin. A resin composition containing a resin (Q).
The mass ratio ((Q) / (P)) of the content of the resin (Q) to the content of the cyclic olefin copolymer (P) in the resin composition is 0.1 or more and 5 or less.
The cyclic olefin copolymer (P) is
The repeating unit (a) derived from at least one α-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 resin composition containing the derived repeating unit (b) .
A resin composition in which the resin (Q) contains polyphenylene ether.

(In the above general formula (I), R ³⁰⁰ represents 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. .) In the resin composition according to claim 1 ,
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
At least one non-conjugated unit selected from the group consisting of a repeating unit represented by the following general formula (V), a repeating unit represented by the following general formula (VI), and a repeating unit represented by the following general formula (VII). A resin composition in which the content of the repeating unit (c) derived from a diene-based olefin is 0.05 mol% or less.

(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.) In the resin composition according to claim 1 or 2 .
The repeating unit (a) derived from the α-olefin in the cyclic olefin copolymer (P) is a linear hydrocarbon group having R ³⁰⁰ having 2 or more and 10 or less carbon atoms in the general formula (I). A resin composition containing a repeating unit. In the resin composition according to any one of claims 1 to 3 .
The repeating unit (b) derived from the cyclic olefin in the cyclic olefin copolymer (P) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] -3-A resin composition which is a repeating unit derived from at least one compound selected from dodecene. In the resin composition according to any one of claims 1 to 4 .
When the total of the repeating units contained in the cyclic olefin copolymer (P) is 100 mol%,
A resin composition in which the content of the repeating unit (b) derived from the cyclic olefin is 10 mol% or more and 90 mol% or less. In the resin composition according to any one of claims 1 to 5 .
Heat-resistant stabilizer, weather-resistant stabilizer, radiation-resistant agent, plasticizer, lubricant, mold release agent, nucleating agent, friction abrasion improver, flame retardant, foaming agent, antistatic agent, colorant, antifogging agent, anti-blocking agent A resin composition further comprising one or more additives selected from the group consisting of impact resistant agents, surface wetting improvers, fillers, hydrochloric acid absorbents, metal deactivators and curing accelerators. A varnish containing the resin composition and solvent according to any one of claims 1 to 6 . The crosslinked product of the resin composition according to any one of claims 1 to 6 . A film or sheet containing the crosslinked product according to claim 8 . A laminate in which the film or sheet according to claim 9 is laminated on a base material. A circuit board including an electrically insulating layer including the crosslinked body according to claim 8 and a conductor layer provided on the electrically insulating layer. The electronic device provided with the circuit board according to claim 11 . A prepreg containing the resin composition according to any one of claims 1 to 6 and a sheet-like fiber base material. A multilayer molded product or a multilayer laminated film in which the resin composition according to any one of claims 1 to 6 is formed on a surface layer having a thickness of 100 μm or less.