JP2019011430A - Cyclic olefinic copolymer composition and crosslinked body thereof - Google Patents

Abstract

To provide a cyclic olefinic copolymer composition that can improve thermal aging resistance while maintaining excellent dielectric properties of a cyclic olefinic copolymer.SOLUTION: A cyclic olefinic copolymer composition contains a cyclic olefinic copolymer (m), and a hindered amine compound (Y) having a piperidyl group. The cyclic olefinic copolymer (m) contains (A) at least one olefin-derived repeating unit represented by a specific structural formula, (B) at least one cyclic non-conjugated diene-derived repeating unit represented by a specific structural formula, and (C) at least one cyclic olefin-derived repeating unit represented by a specific structural formula, at specific ratios. When the content of the cyclic olefinic copolymer (m) contained in the cyclic olefinic copolymer composition is 100 pts.mass, the content of the hindered amine compound (Y) in the cyclic olefinic copolymer composition is 0.01 pts.mass or more and 5 pts.mass or less.SELECTED DRAWING: None

Description

  The present invention relates to a cyclic olefin copolymer composition and a crosslinked product thereof.

  Cyclic olefin-based copolymers are excellent in heat resistance, mechanical properties, transparency, dielectric properties, solvent resistance, moldability, dimensional stability, etc., and thus are used in various fields (for example, patent documents). 1 and 2).

  In recent years, cyclic olefin-based polymers are excellent in the balance between heat resistance and dielectric properties, and thus have begun to be examined as materials for electronic parts such as printed wiring boards (for example, Patent Documents 2 and 3). reference).

  Patent Document 2 describes a cyclic olefin copolymer having a crosslinkable group. This crosslinked product of cyclic olefin copolymer is excellent in stability over time of dielectric properties and heat resistance, transparency, mechanical properties, etc., so it should be used suitably for high frequency applications such as high frequency circuit boards. It is stated that you can.

  Patent Document 3 describes a crosslinkable resin composition comprising a cyclic olefin resin, an organic peroxide, a crosslinking aid and powdered red phosphorus. The cross-linked resin molded product obtained by heating and cross-linking this cross-linkable resin composition has dielectric properties in the high frequency band and solder heat resistance, and has high flame retardancy and high mechanical strength. It is described that it can be suitably used for applications requiring dielectric properties, heat resistance, flame retardancy, mechanical properties, etc., such as printed wiring boards and computer parts.

International Publication No. 2006/118261 International Publication No. 2012/046443 JP-A-2005-47992

According to the study by the present inventors, a crosslinked product composed of a cyclic olefin copolymer having a crosslinkable group as described in Patent Document 2 gradually exhibits dielectric properties when exposed to high temperatures. It became clear that it got worse. That is, the crosslinked body comprised with the cyclic olefin type copolymer which has a crosslinkable group was inferior to heat aging resistance.
Moreover, the crosslinked body comprised by cyclic olefin resin as described in patent document 3 does not have a crosslinkable group in the cyclic olefin resin which is a main component of the resin composition which comprises this crosslinked body. Therefore, the crosslinking reactivity is inferior, and there is room for improvement in terms of heat resistance.
Furthermore, according to the study by the present inventors, in order to improve the heat aging resistance of a crosslinked body composed of a cyclic olefin copolymer having a crosslinkable group as described in Patent Document 2, It has become clear that increasing the amount of the heat stabilizer added to the olefin copolymer may deteriorate the dielectric properties.
From the above, there is room for improvement in the cross-linked product composed of the cyclic olefin copolymer having a crosslinkable group in terms of improving the heat aging resistance while maintaining the excellent dielectric properties of the cyclic olefin copolymer. was there.

  The present invention has been made in view of the above circumstances, and provides a cyclic olefin copolymer composition capable of improving heat aging resistance while maintaining excellent dielectric properties of the cyclic olefin copolymer. It is.

  As a result of intensive studies to solve the above problems, the present inventors have mixed a hindered amine compound having a specific piperidyl group at a specific ratio with a cyclic olefin copolymer having a crosslinkable group. The present inventors have found that the heat aging resistance is improved while maintaining the excellent dielectric properties of the cyclic olefin copolymer, thereby completing the present invention.

  The present invention is as follows.

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

〔上記一般式（III）中、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。〕

〔上記一般式（Ｖ）中、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（１）において、Ｘは水素原子、オキシラジカル基、アルキル基、アルコキシ基、アリール基、またはヒドロキシ基であり、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立に水素原子、またはアルキル基である。〕
［２］
上記環状非共役ジエン由来の繰り返し単位（Ｂ）を構成する環状非共役ジエンが、５−ビニル−２−ノルボルネンまたは８−ビニル−９−メチルテトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセンである上記［１］に記載の環状オレフィン系共重合体組成物。
［３］
上記環状オレフィン由来の繰り返し単位（Ｃ）を構成する環状オレフィンが、ビシクロ［２．２．１］−２−ヘプテンまたはテトラシクロ［４．４．０．１^２，５．１^７，１０]−３−ドデセンである上記［１］または［２］に記載の環状オレフィン系共重合体組成物。
［４］
上記環状オレフィン系共重合体（ｍ）とは異なる環状オレフィン系重合体（ｎ）をさらに含み、
上記環状オレフィン系重合体（ｎ）は、エチレンまたはα−オレフィンと環状オレフィンとの共重合体（ｎ１）（ただし、上記共重合体（ｎ１）は下記一般式（III）で表される環状非共役ジエン由来の繰り返し単位を含まない）および環状オレフィンの開環重合体（ｎ２）から選択される少なくとも一種を含み、
上記環状オレフィン系共重合体（ｍ）と上記環状オレフィン系重合体（ｎ）との合計量を１００質量％としたとき、
上記環状オレフィン系共重合体（ｍ）の含有量が５質量％以上９５質量％以下であり、上記環状オレフィン系重合体（ｎ）の含有量が５質量％以上９５質量％以下である上記［１］乃至［３］のいずれか一つに記載の環状オレフィン系共重合体組成物。

〔上記一般式（III）中、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７６ならびにＲ^ａ１およびＲ^ｂ１は互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^１０４は水素原子または炭素原子数１〜１０のアルキル基であり、tは０〜１０の正の整数であり、Ｒ^７５およびＲ^７６は互いに結合して単環または多環を形成していてもよい。〕
［５］
上記ヒンダートアミン系化合物（Ｙ）の分子量は１０００以上である上記［１］乃至［４］のいずれか一つに記載の環状オレフィン系共重合体組成物。
［６］
上記［１］乃至［５］のいずれか一つに記載の環状オレフィン系共重合体組成物と溶媒を含有するワニス。
［７］
上記［１］乃至［５］のいずれか一つに記載の環状オレフィン系共重合体組成物の架橋体。
［８］
上記［７］に記載の架橋体を含むフィルムまたはシート。
［９］
上記［８］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。
［１０］
上記［１］乃至［５］のいずれか一つに記載の環状オレフィン系共重合体組成物とシート状繊維基材とを含むプリプレグ。
［１１］
上記［８］に記載のフィルムまたはシート、上記［９］に記載の積層体、および上記［１０］に記載のプリプレグから選択される少なくとも一種と、金属箔と、を積層してなる金属張積層板。
［１２］
上記［８］に記載のフィルムまたはシート、上記［９］に記載の積層体、および上記［１０］に記載のプリプレグから選択される少なくとも一種により形成された電気絶縁層と、上記電気絶縁層上に設けられた導体層とを備えるプリント配線基板。
［１３］
上記［１２］に記載のプリント配線基板を備えた電子機器。 [1]
A cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and a hindered amine compound (Y) having a piperidyl group represented by the following general formula (1):
The cyclic olefin copolymer (m) is
(A) a repeating unit derived from one or more olefins represented by the following general formula (I);
(B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III):
(C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V),
When the total number of repeating units in the cyclic olefin-based copolymer (m) is 100 mol%, the content of the repeating unit (A) derived from the olefin is 10 mol% or more and 90 mol% or less, The content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 30 mol% or less,
When the content of the cyclic olefin copolymer (m) contained in the cyclic olefin copolymer composition is 100 parts by mass, the hindered amine compound in the cyclic olefin copolymer composition. The cyclic olefin copolymer composition whose content of (Y) is 0.01 mass part or more and 5 mass parts or less.

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

[In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. A monocyclic ring or a polycyclic ring may be formed. ]

[In the general formula (V), 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. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 aromatic hydrocarbon groups, R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. ]

[In the general formula (1), X is a hydrogen atom, an oxy radical group, an alkyl group, an alkoxy group, an aryl group, or a hydroxy group, and R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom. Or an alkyl group. ]
[2]
The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene is 5-vinyl-2-norbornene or 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . The cyclic olefin copolymer composition according to the above [1], which is 1 ^7,10 ] -3-dodecene.
[3]
The cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin is bicyclo [2.2.1] -2-heptene or tetracyclo [4.4.0.1 ^2,5 . The cyclic olefin copolymer composition according to the above [1] or [2], which is 1 ^7,10 ] -3-dodecene.
[4]
A cyclic olefin polymer (n) different from the cyclic olefin copolymer (m);
The cyclic olefin polymer (n) is a copolymer (n1) of ethylene or α-olefin and a cyclic olefin (wherein the copolymer (n1) is a cyclic non-polymer represented by the following general formula (III): Including no repeating unit derived from a conjugated diene) and a ring-opening polymer of cyclic olefin (n2),
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) is 100% by mass,
The cyclic olefin copolymer (m) content is 5% by mass or more and 95% by mass or less, and the cyclic olefin polymer (n) content is 5% by mass or more and 95% by mass or less. [1] The cyclic olefin copolymer composition according to any one of [3].

[In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. A monocyclic ring or a polycyclic ring may be formed. ]
[5]
The cyclic olefin copolymer composition according to any one of [1] to [4], wherein the hindered amine compound (Y) has a molecular weight of 1000 or more.
[6]
A varnish containing the cyclic olefin copolymer composition according to any one of [1] to [5] above and a solvent.
[7]
A crosslinked product of the cyclic olefin copolymer composition according to any one of [1] to [5].
[8]
A film or sheet comprising the crosslinked product according to the above [7].
[9]
The laminated body which laminated | stacked the film or sheet as described in said [8] on the base material.
[10]
A prepreg comprising the cyclic olefin copolymer composition according to any one of [1] to [5] above and a sheet-like fiber base material.
[11]
Metal-clad laminate obtained by laminating at least one selected from the film or sheet according to [8] above, the laminate according to [9] above, and the prepreg according to [10] above, and a metal foil. Board.
[12]
An electrical insulating layer formed of at least one selected from the film or sheet described in [8] above, the laminate described in [9] above, and the prepreg described in [10] above, on the electrical insulating layer A printed wiring board comprising a conductor layer provided on the board.
[13]
Electronic equipment provided with the printed wiring board according to [12] above.

  According to the present invention, it is possible to provide a cyclic olefin copolymer composition capable of improving the heat aging resistance while maintaining the excellent dielectric properties of the cyclic olefin copolymer.

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

First, the cyclic olefin type copolymer composition of embodiment which concerns on this invention is demonstrated.
The cyclic olefin copolymer composition according to the present embodiment contains a cyclic olefin copolymer (m) and a hindered amine compound (Y).
When the content of the cyclic olefin copolymer (m) contained in the cyclic olefin copolymer composition according to this embodiment is 100 parts by mass, the hindered amine in the cyclic olefin copolymer composition is The content of the system compound (Y) is 0.01 parts by mass or more, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, and particularly preferably 0.08 parts by mass or more. . When the content of the hindered amine compound (Y) is not less than the above lower limit, the heat aging resistance of the cyclic olefin copolymer composition can be improved.
Further, when the content of the cyclic olefin copolymer (m) contained in the cyclic olefin copolymer composition according to this embodiment is 100 parts by mass, the hint in the cyclic olefin copolymer composition is reduced. The content of the dartamine compound (Y) is 5 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less. When the content of the hindered amine compound (Y) is not more than the above upper limit value, it is possible to suppress a decrease in the dielectric properties of the cyclic olefin copolymer composition.

The total content of the cyclic olefin-based polymer contained in the cyclic olefin-based copolymer composition according to the present embodiment is preferably 20 mass when the entire cyclic olefin-based copolymer composition is 100 mass%. % Or more, more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 60% by mass or more. Thereby, the balance of heat resistance, mechanical properties, transparency, dielectric properties, solvent resistance, moldability, dimensional stability, and the like can be improved. Although the upper limit of the total content of the cyclic olefin polymer contained in the cyclic olefin copolymer composition according to this embodiment is not particularly limited, for example, it is less than 100% by mass, preferably 99% by mass or less. .
Here, the cyclic olefin polymer contained in the cyclic olefin copolymer composition according to the present embodiment means a cyclic olefin copolymer (m) and a cyclic olefin copolymer (n) described later. To do.

  Hereinafter, each component will be specifically described.

[Cyclic olefin copolymer (m)]
The cyclic olefin copolymer (m) according to the present embodiment includes (A) one or more olefin-derived repeating units represented by the following general formula (I), and (B) the following general formula (III). The repeating unit derived from the 1 or more types of cyclic nonconjugated diene represented, and the repeating unit derived from the 1 or more types of cyclic olefin represented by (C) following general formula (V).

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

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

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

In the cyclic olefin copolymer (m), when the total number of repeating units in the cyclic olefin copolymer (m) is 100 mol%, the content of the olefin-derived repeating unit (A) is 10%. Mol% or more and 90 mol% or less, preferably 15 mol% or more and 85 mol% or less, more preferably 20 mol% or more and 80 mol% or less, still more preferably 30 mol% or more and 80 mol% or less, and even more preferably 35 mol%. 80 mol% or less, particularly preferably 40 mol% or more and 80 mol% or less, and the content of the repeating unit (B) derived from the cyclic nonconjugated diene is 1 mol% or more and 40 mol% or less, preferably 2 mol% or more. 35 mol% or less, more preferably 3 mol% or more and 30 mol% or less, and the content of the cyclic olefin-derived repeating unit (C) is 1 mol% or more and 30 mol% Lower, preferably 3 mol% to 25 mol% or less, further preferably 20 mol% or less than 5 mol%.
When the content of each repeating unit in the cyclic olefin copolymer (m) is within the above range, the crosslinked product obtained from the cyclic olefin copolymer composition has excellent stability over time of dielectric properties. It also has excellent heat resistance. Furthermore, a crosslinked product (Q) excellent in mechanical properties, dielectric properties, transparency and gas barrier properties can be obtained. In other words, a crosslinked product (Q) having an excellent balance of these physical properties can be obtained.

  The olefin monomer, which is one of the copolymer raw materials of the cyclic olefin copolymer (m), is a monomer that gives a skeleton represented by the above formula (I) by addition copolymerization, and is represented by the following general formula (Ia): It is an olefin represented.

In the general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl. -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. Among these, ethylene and propylene are preferable, and ethylene is particularly preferable from the viewpoint of obtaining a crosslinked body (Q) having more excellent heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties. Two or more types of olefin monomers represented by the above formula (Ia) may be used.

  The cyclic non-conjugated diene monomer, which is one of the copolymer raw materials of the cyclic olefin copolymer (m), is addition-copolymerized to form the structural unit represented by the above formula (III). Specifically, a cyclic nonconjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.

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

The cyclic nonconjugated diene represented by the general formula (IIIa) is not particularly limited, and examples thereof include cyclic nonconjugated dienes represented by the following chemical formula. Of these, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

  The cyclic non-conjugated diene represented by the general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

N in the general formula (IIIb) is an integer of 0 to 10, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. It is.

  The cyclic olefin copolymer (m) according to the present embodiment contains a structural unit derived from the cyclic nonconjugated diene represented by the general formula (III), whereby a side chain portion, that is, a main chain of copolymerization. It has the characteristic that it has a double bond in other parts.

  The cyclic olefin monomer which is one of the copolymer raw materials of the cyclic olefin copolymer (m) is addition-copolymerized to form the structural unit represented by the above formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

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

About the specific example of the cyclic olefin represented by the said general formula (Va), the compound as described in international publication 2006/118261 can be used.
Examples of the cyclic olefin represented by the general formula (Va) include bicyclo [2.2.1] -2-heptene (also referred to as norbornene), tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (also referred to as tetracyclododecene) is preferred, and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is more preferred. Since these cyclic olefins have a rigid ring structure, it is easy to maintain the elastic modulus of the copolymer and the crosslinked product, and since they do not contain a heterogeneous double bond structure, there is an advantage that the crosslinking can be easily controlled.

  By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as a copolymerization component, the solubility of the cyclic olefin copolymer (m) in a solvent is increased. Improves the moldability and improves the yield of the product.

The cyclic olefin copolymer (m) is derived from (A) one or more olefin-derived repeating units represented by the general formula (I), and (B) derived from a cyclic non-conjugated diene represented by the general formula (III). In addition to the repeating unit of (C) and one or more cyclic olefin-derived repeating units represented by the general formula (V), the cyclic non-conjugated diene represented by the general formula (III) and the general formula (V) It may be composed of a cyclic olefin other than the cyclic olefin represented and / or a repeating unit derived from a chain polyene.
In this case, as a copolymer raw material of the cyclic olefin copolymer (m), an olefin monomer represented by the general formula (Ia), a cyclic non-conjugated diene monomer represented by the general formula (IIIa), and a general formula (Va) In addition to the cyclic olefin monomer represented by general formula (IIIa), a cyclic non-conjugated diene monomer represented by general formula (IIIa) and a cyclic olefin monomer other than the cyclic olefin monomer represented by general formula (Va), and / or a chain polyene Monomers can be used.
Such a cyclic olefin monomer and a chain polyene monomer are a cyclic olefin represented by the following general formula (VIa) or (VIIa), or a chain polyene represented by the following general formula (VIIIa). Two or more different cyclic olefins and chain polyenes may be used.

In the general formula (VIa), x and d are 0 or an integer of 1 or more, preferably 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R ⁸¹ ˜R ⁹⁹ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group that is a cycloalkyl group having 3 to 15 carbon atoms, the number of carbon atoms 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, which is an aromatic hydrocarbon group or alkoxy group of 6 to 20 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 to form a single ring. Or polycyclic fragrance It may form a ring.

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

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

  About the specific example of the cyclic olefin represented by general formula (VIa) and general formula (VIIa), the compound as described in the paragraphs 0037-0063 of international publication 2006/118261 can be used.

  Specific examples of the chain polyene represented by the general formula (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 , 4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene and the like. A cyclizable polyene cyclized from a polyene such as 1,3-butadiene and 1,5-hexadiene may also be used.

  The cyclic olefin copolymer (m) is a structural unit derived from a chain polyene represented by the general formula (VIIIa), or a cyclic non-conjugated diene represented by the general formula (III) and the general formula (V). When a structural unit derived from a cyclic olefin other than the cyclic olefin represented (for example, general formula (VIa), general formula (VIIa)) is included, the content of the structural unit is represented by the above general formula (I). One or more olefin-derived repeating units, one or more cyclic non-conjugated diene-derived repeating units represented by the above general formula (III), and one or more cyclic groups represented by the above general formula (V) It is 0.1-100 mol% normally with respect to the total mole number of the repeating unit derived from an olefin, Preferably it is 0.1-50 mol%.

  As the copolymer component, the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the chain polyene represented by the general formula (VIIIa) are used. Thus, the effects of the present embodiment can be obtained, and the solubility of the cyclic olefin copolymer in the solvent is further improved, so that the moldability is improved and the yield of the product is improved. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferable. Since these cyclic olefins have a rigid ring structure, it is easy to maintain the elastic modulus of the copolymer and the crosslinked product, and since they do not contain a heterogeneous double bond structure, there is an advantage that the crosslinking can be easily controlled.

  The cyclic olefin copolymer (m) can control the comonomer content and the glass transition point (Tg) according to the charge ratio of the monomers according to the intended use. The Tg of the cyclic olefin copolymer (m) is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, even more preferably 170 ° C. or lower, and particularly preferably 150 ° C. or lower. When the Tg is not more than the above upper limit, the melt moldability of the cyclic olefin copolymer (m) and the solubility in a solvent when varnishing are improved.

The intrinsic viscosity [η] of the cyclic olefin copolymer (m) measured in decalin at 135 ° C. is usually 0.10 to 15 dl / g, preferably 0.10 to 5 dl / g, more preferably 0.8. The range is 15 to 3 dl / g. When the intrinsic viscosity [η] is not more than the above upper limit value, the moldability is improved. Further, when the intrinsic viscosity [η] is not less than the above lower limit, the heat resistance and mechanical properties of the crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer composition are improved.
The intrinsic viscosity [η] of the cyclic olefin copolymer (m) can be controlled by polymerization conditions such as a polymerization catalyst, a cocatalyst, the amount of H ₂ added, and a polymerization temperature.

[Method for Producing Cyclic Olefin Copolymer (m)]
The cyclic olefin copolymer (m) according to the present embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012/046443. Details are omitted here.

[Hinder amine compound (Y)]
The hindered amine compound (Y) according to the present embodiment is a compound having a piperidyl group represented by the following general formula (1). The number of piperidyl groups represented by the general formula (1) per molecule may be one or plural.

上記一般式（１）において、Ｘは水素原子、オキシラジカル基、アルキル基、アルコキシ基、アリール基、またはヒドロキシ基であり、好ましくは水素原子、メチル基またはエチル基であり、より好ましくは水素原子またはメチル基であり、特に好ましくは水素原子である。
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立に水素原子またはアルキル基であり、好ましくはメチル基またはエチル基であり、より好ましくはメチル基である。

In the general formula (1), X is a hydrogen atom, an oxy radical group, an alkyl group, an alkoxy group, an aryl group, or a hydroxy group, preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom. Or a methyl group, particularly preferably a hydrogen atom.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group.

  In the above general formula (1), the number of carbon atoms when X is an alkyl group is preferably 1-12, the number of carbon atoms when X is an alkoxy group is preferably 1-12, and the number of carbon atoms when X is an aryl group is 6-12 are preferable. The alkyl group or alkoxy group represented by X is independently linear or cyclic, and may have a branched chain. Further, the alkyl group, alkoxy group or aryl group represented by X may each independently have a substituent, and examples of the substituent include a hydroxy group, a benzoyloxy group, an acetoxy group and the like.

Of the piperidyl groups represented by the general formula (1), compounds having groups in which R ¹ , R ² , R ³ and R ⁴ are all methyl groups are preferred from the viewpoint of price and availability. Moreover, the compound which has a piperidyl group whose X is a methyl group or a hydrogen atom is preferable from a point of price or availability.

  Moreover, as a hindered amine type compound (Y) which has a piperidyl group represented by the said General formula (1), the compound which has two or more piperidyl groups in 1 molecule is preferable. In that case, a compound in which two or more piperidyl groups are bonded via a bond at the 4-position of the piperidyl group represented by the general formula (1) is preferable.

The molecular weight of the hindered amine compound (Y) according to this embodiment is preferably 140 or more and 20000 or less. When the molecular weight of the hindered amine compound (Y) is in the above range, the volatilization during processing is small and it is easy to mix well with other components, and the cyclic olefin copolymer composition according to the present embodiment A decrease in fluidity can also be suppressed.
Further, the hindered amine compound (Y) according to this embodiment may be a low molecular weight type or a high molecular weight type. The molecular weight of the low molecular weight type hindered amine compound (Y) is preferably 200 or more and less than 1000, and the molecular weight of the high molecular weight type hindered amine compound (Y) is preferably 1000 or more and 20000 or less. More preferably, it is 1000 or more and 10,000 or less.
In particular, it is preferable that the molecular weight of the hindered amine compound (Y) is 1000 or more because volatilization during processing is further reduced and mixing with other components is easier.
The molecular weight of the hindered amine compound (Y) can be measured as the relative mass of the molecule by, for example, a mass spectrometer.

  The hindered amine compound (Y) according to the present embodiment may have a radical scavenging action. Thereby, the radical generated by the heat and light received under the usage environment of the molded product is captured during the production and molding of the cyclic olefin copolymer composition according to the present embodiment, and the cyclic during the production and molding Oxidative deterioration and thermal decomposition of the olefin polymer can be suppressed, and oxidation deterioration and decomposition of the cyclic olefin polymer in the molded product due to heat and light can be suppressed.

The hindered amine compound (Y) according to the present embodiment is not limited to the following. For example, 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6 -Tetramethyl-4-piperidinol; bis- (1,2,2,6,6-pentamethylpiperidyl)-(3 ', 5'-di-t-butyl-4'-hydroxybenzyl) butyl malonate; -(2,2,6,6-tetramethyl-4-piperidyl) sebacate; oligomer of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid; cyanuric acid And N, N-di (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine oligomer; bis- (2,2,6,6-tetramethyl-4-piperidinyl) succinate; bis − 1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate; bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; tetrakis- (2,2, 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate; N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexane -1,6-diamine; N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2 ′-[(2,2,6,6-tetramethyl-piperidinyl) -imino] -Bis- [ethanol]; poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) -iminohexamethylene- (2,2, 6,6-tetramethyl 4- (piperidinyl) -imino); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cyclo-undecyl-oxazole); 1,1 ′-(1,2-ethane- Di-yl) -bis- (3,3 ′, 5,5′-tetramethyl-piperazinone); 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4.5) Decane-2,4-dione; polymethylpropyl-3-oxy- [4 (2,2,6,6-tetramethyl) -piperidinyl] siloxane; 1,2,3,4-butane- Tetracarboxylic acid-1,2,3-tris (1,2,2,6,6-pentamethyl-4-piperidinyl) -4-tridecyl ester; α-methylstyrene-N- (2,2,6,6) -Tetramethyl-4-piperidinyl) maleimide and N Stearylmaleimide copolymer; 1,2,3,4-butanetetracarboxylic acid, β, β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3 , 9-diethanol, polymer with 1,2,2,6,6-pentamethyl-4-piperidinyl ester; 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, Β, β, β ′, β′-tetramethyl-polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester; D-glucitol, 1,3: 2,4-bis-o- (2,2,6,6-tetramethyl-4-piperidinylidene)-; 7-oxa-3,20-diazadispiro [5.1.1.12 ] -Henikosan-21-on-2, , 4,4-tetramethyl-20- (oxiranylmethyl) oligomer; propanedioic acid, [(4-methoxyphenyl) methylene]-, bis (1,2,2,6,6-pentamethyl-4- Piperidinyl) ester; formamide, N, N′-1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl; 1,3,5-triazine-2,4,6 Triamine, N, N ″ ′-[1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl-4-piperidinyl) amino] -1,3 5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ′, N ″ -dibutyl-N ′, N ″ -bis (1,2,2,6,6- Pentamethyl-4-piperidinyl); poly [6- (1,1,3,3-te Lamethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]; 1,5-dioxaspiro (5.5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-piperidinyl) ester; 1,5- Dioxaspiro (5.5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester; N-2,2,6,6-tetramethyl-4-piperidinyl -N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; 1,5,8,12-tetrakis [2 ', 4'-bis (1 ", 2 '', 2 '' , 6 ″, 6 ″ -pentamethyl-4 ″ -piperidinyl (butyl) amino) -1 ′, 3 ′, 5′-triazin-6′-yl] -1,5,8,12-tetraazadodecane 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione; 1,1 ′-(1,2-ethane-di-yl) -bis -(3,3 ', 5,5'-tetra-methyl-piperazinone);1,1'1"-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2 , 1-ethanediyl) tris (3,3,5,5-tetramethylpiperazinone); 1,1 ′, 1 ″-(1,3,5-triazine-2,4,6-triyltris ((cyclohexyl) Imino) -2,1-ethanediyl) tris (3,3,4,5,5-tetramethylpiperazinone And dibutylamine 1,3,5-triazine.N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (2,2,6) , 6-tetramethyl-4-piperidyl) butylamine polycondensate and the like.
Among these, 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, CHIMASSORB944FDL, manufactured by BASF), and dibutylamine 1,3,5-triazine N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate At least one selected from (for example, CHIMASSORB2020FDL, manufactured by BASF) is preferable.

[Cyclic olefin polymer (n)]
The cyclic olefin copolymer composition according to the present embodiment may further include a cyclic olefin polymer (n) different from the cyclic olefin copolymer (m).
Specifically, the cyclic olefin polymer (n) includes at least one selected from a copolymer (n1) of ethylene or an α-olefin and a cyclic olefin, and a ring-opened polymer (n2) of the cyclic olefin. . The cyclic olefin copolymer composition according to the present embodiment includes the cyclic olefin polymer (n), thereby further improving the dielectric properties of the crosslinked product obtained by crosslinking the cyclic olefin copolymer composition. It can be good.
Here, the copolymer (n1) does not contain a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III). In this embodiment, the said copolymer (n1) does not contain the repeating unit derived from the cyclic | annular nonconjugated diene represented by the said general formula (III) means the sum total of the repeating unit in the said copolymer (n1). When the number of moles is 100 mol%, it means that the content of the repeating unit derived from the cyclic nonconjugated diene represented by the general formula (III) is 0.05 mol% or less.
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) contained in the cyclic olefin copolymer composition according to this embodiment is 100% by mass, the cyclic olefin copolymer is used. The content of the polymer (m) is 5% by mass to 95% by mass, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 25% by mass to 75% by mass. %, And the content of the cyclic olefin polymer (n) is 5% by mass to 95% by mass, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, Preferably they are 25 mass% or more and 75 mass% or less.

  As a copolymer (n1) of ethylene or an α-olefin and a cyclic olefin, for example, the polymers described in paragraphs 0030 to 0123 of International Publication No. 2008/047468 can be used.

  For example, a polymer having an alicyclic structure in at least a part of repeating structural units (hereinafter, also simply referred to as “polymer having an alicyclic structure”), and an alicyclic ring in at least a part of the repeating units of the polymer. Any polymer having a group structure may be used, and specifically, a polymer having one or more types of structures represented by the following general formula (3) is preferably included.

（式（３）中、ｘ、ｙは共重合比を示し、０／１００≦ｙ／ｘ≦９５／５を満たす実数である。ｘ、ｙはモル基準である。
ｎは置換基Ｑの置換数を示し、０≦ｎ≦２の実数である。
Ｒ^ａは、炭素原子数２〜２０の炭化水素基よりなる群から選ばれる２＋ｎ価の基である。
Ｒ^ｂは、水素原子、又は炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基である。
Ｒ^ｃは、炭素原子数２〜１０の炭化水素基よりなる群から選ばれる４価の基である。
Ｑは、ＣＯＯＲ^ｄ（Ｒ^ｄは、水素原子、または炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基である。）である。
Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃおよびＱは、それぞれ１種であってもよく、２種以上を任意の割合で有していてもよい。）

(In formula (3), x and y represent copolymerization ratios and are real numbers satisfying 0/100 ≦ y / x ≦ 95/5. X and y are on a molar basis.
n represents the number of substitutions of the substituent Q, and is a real number of 0 ≦ n ≦ 2.
R ^a is a 2 + n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms.
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms.
Q is COOR ^d (R ^d is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).
Each of R ^a , R ^b , R ^c and Q may be one kind, or may have two or more kinds in any ratio. )

In the general formula (3), R ^a is preferably one or more divalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, and more preferably n = 0. In this case, it is a divalent group represented by the following general formula (7), and most preferably a divalent group in which p is 0 or 1 in the following general formula (7). The structure of ^Ra may be used alone or in combination of two or more.

ここで、式（７）中、ｐは、０〜２の整数である。

Here, in Formula (7), p is an integer of 0-2.

  The copolymer (n1) of ethylene or α-olefin and cyclic olefin is a cyclic olefin copolymer represented by the following general formula (4). For example, it consists of a structural unit (A) derived from a linear or branched α-olefin having 3 to 30 carbon atoms and a structural unit (B) derived from a cyclic olefin.

（式（４）中、Ｒ^ａは、炭素原子数２〜２０の炭化水素基よりなる群から選ばれる２価の基である。
Ｒ^ｂは、水素原子、または炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基である。
Ｒ^ａおよびＲ^ｂは、それぞれ１種であってもよく、２種以上を任意の割合で有していてもよい。
ｘ、ｙは共重合比を示し、５／９５≦ｙ／ｘ≦９５／５を満たす実数である。好ましくは５０／５０≦ｙ／ｘ≦９５／５、さらに好ましくは、５５／４５≦ｙ／ｘ≦８０／２０である。ｘ、ｙはモル基準である。

(In Formula (4), ^Ra is a bivalent group chosen from the group which consists of a C2-C20 hydrocarbon group.
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Each of R ^a and R ^b may be one type, or may have two or more types in any proportion.
x and y represent copolymerization ratios and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. Preferably 50/50 ≦ y / x ≦ 95/5, and more preferably 55/45 ≦ y / x ≦ 80/20. x and y are on a molar basis.

The copolymer (n1) of ethylene or α-olefin and a cyclic olefin is preferably a copolymer comprising ethylene and a cyclic olefin, and the cyclic olefin is bicyclo [2.2.1] -2-heptene or tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct and cyclopentadiene-acenaphthylene adduct Those described above are preferable, and bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . More preferred is at least one selected from 1 ^7,10 ] -3-dodecene.
The copolymer (n1) of ethylene or α-olefin and cyclic olefin is a polymer having one or more structures represented by the general formula (3) or the general formula (4). The expressed cyclic olefin copolymer may be a hydrogenated polymer.

As the copolymer (n1) of ethylene or α-olefin and a cyclic olefin, a copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin is also preferable. Examples of the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin include the polymers described in paragraphs 0056 to 0070 of International Publication No. 2015/178145.
Examples of the cyclic olefin constituting the copolymer of the α-olefin having 4 to 12 carbon atoms and the cyclic olefin include norbornene and substituted norbornene, and norbornene is preferable. The said cyclic olefin can be used individually by 1 type or in combination of 2 or more types.

  The substituted norbornene is not particularly limited, and examples of the substituent that the substituted norbornene has include a halogen atom, a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (A).

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。ただし、ｎ＝０の場合、Ｒ^１〜Ｒ^４及びＲ^９〜Ｒ^１２の少なくとも１つは、水素原子ではない。）

(In the formula, R ^{1 to} R ¹² may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁹ , R ¹⁰ , R ^11, and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, and n is 0 or a positive integer, and when n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit, provided that when n = 0, R 5 ^At least one of ^{1 to} R ⁴ and R ^{9 to} R ¹² is not a hydrogen atom.)

The substituted norbornene represented by the general formula (A) will be described. R ^{1 to} R ¹² in the general formula (A) may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ^{1 to} R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , May be partially different or all may be the same.

Specific examples of R ^{9 to} R ¹² include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and tolyl Group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group and the like substituted or unsubstituted aromatic hydrocarbon group; benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group These may be different from each other, may be partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the general formula (A) include 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hepta- 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2. 1] Hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [ 2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5- Bicyclic rings such as propenyl-bicyclo [2.2.1] hept-2-ene Olefin; tricyclo [4.3.0.1 ^{2, 5]} deca-3,7-diene (trivial name: dicyclopentadiene), tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene; Tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or Tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, which is an adduct of cyclopentadiene and cyclohexene); 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl -Bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene 3 ring Olefin; tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo [4,4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . Tetracyclic olefins such as 1 ^7,10 ] dodec-3-ene; 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; tetracyclo [7.4.1 ^3,6 . 0 ^1,9 . 0 ^2,7 ] tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^4,7 . 0 ^1,10 . 0 ^3,8 ] pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); pentacyclo [6.6.1]. ^.1,3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.0 ^2,7. 1 ^3,6 . 1 ^10,13] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, heptacyclo [8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^4,7 . 0 ^12,17 . 1 ^13,16 ] ^-14-eicosene ; and polycyclic cyclic olefins such as cyclopentadiene tetramer.

  Among them, alkyl-substituted norbornene (eg, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornene (eg, bicyclo substituted with one or more alkylidene groups) [2.2.1] hept-2-ene) is preferred, 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene Is particularly preferred.

  Examples of the α-olefin having 4 to 12 carbon atoms constituting the copolymer of the α-olefin having 4 to 12 carbon atoms and the cyclic olefin include at least a α-olefin having 4 to 12 carbon atoms and a halogen atom. The C4-C12 alpha-olefin which has 1 type of substituent is mentioned, A C4-C12 alpha-olefin is preferable.

  The α-olefin having 4 to 12 carbon atoms is not particularly limited. For example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Examples include 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Of these, 1-hexene, 1-octene and 1-decene are preferable.

The copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin according to this embodiment has 4 to 12 carbon atoms when the total number of repeating units contained in the copolymer is 100 mol%. The proportion of the repeating unit derived from α-olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 80 mol% or less, and further preferably 20 mol% or more and 70 mol% or less.
In addition, the copolymer of the α-olefin having 4 to 12 carbon atoms and the cyclic olefin according to the present embodiment is derived from the cyclic olefin when the total number of repeating units contained in the copolymer is 100 mol%. The ratio of the repeating unit is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and further preferably 30 mol% or more and 80 mol% or less.

  The conditions of the polymerization step for obtaining a copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin are not particularly limited as long as a desired copolymer is obtained, and known conditions can be used. The polymerization temperature, polymerization pressure, polymerization time, etc. are appropriately adjusted.

Moreover, as the cyclic olefin polymer (n), a cyclic olefin ring-opening polymer (n2) can be used.
Examples of the ring-opening polymer (n2) of the cyclic olefin include, for example, a ring-opening polymer of a norbornene-based monomer and a ring-opening weight of the norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith. And hydrides thereof, and the like.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (having a substituent in the ring), tricyclo [4.3.01, 6.12,5] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name) Methanotetrahydrofluorene: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. In addition, a substituent can have 1 or 2 or more. As a derivative having a substituent in such a ring, for example, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers are used alone or in combination of two or more.

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

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

  In this embodiment, cyclic olefin polymer (n) may be used individually by 1 type, and may use 2 or more types together.

[Resins other than cyclic olefin polymers]
The cyclic olefin copolymer composition according to the present embodiment includes a thermoplastic resin other than the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) within a range not impairing the purpose of the present embodiment. It may further include at least one selected from thermosetting resins.
The content of the resin other than the cyclic olefin polymer is preferably 1 part by mass or more and 50 parts by mass or less when the entire cyclic olefin copolymer composition is 100 parts by mass.
The resin other than the cyclic olefin polymer is not particularly limited as long as it is a thermoplastic resin or a thermosetting resin. For example, one or two kinds selected from styrene elastomers, ethylene / propylene elastomers, and diene elastomers are used. It is preferable to include the above.

Styrenic elastomers include, for example, styrene / conjugated diene block copolymer resins (such as butadiene and isoprene as conjugated dienes), hydrogenated products of styrene / conjugated diene block copolymer resins (such as butadiene and isoprene as conjugated dienes), styrene・ Conjugated dienes and styrene triblock copolymer resins (conjugated diene such as butadiene and isoprene), hydrogenated products of styrene, conjugated dienes and styrene triblock copolymer resins (conjugated dienes such as butadiene and isoprene), etc. Can be mentioned.
Examples of the ethylene / propylene elastomer include ethylene / propylene rubber and ethylene / propylene / diene rubber.
Examples of the diene elastomer include polybutadiene, polyisoprene, styrene / butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, and the like.

[Additive]
Various additives other than the hindered amine compound (Y) may be further added to the cyclic olefin copolymer composition according to the present embodiment, depending on the purpose. The addition amount of the additive is appropriately selected according to the application within a range that does not impair the purpose of the present embodiment.
Examples of the additives include heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction wear improvers, flame retardants, foaming agents, antistatic agents, colorants, anti-proofing agents. Examples thereof include one or more additives selected from the group consisting of a clouding agent, an antiblocking agent, an impact resistance agent, a surface wetting improver, a filler, a hydrochloric acid absorbent, and a metal deactivator.
The cyclic olefin copolymer composition according to this embodiment may contain a heat stabilizer and a weather stabilizer other than the hindered amine compound (Y) as long as the effects of this embodiment are not significantly impaired. The total content of the heat stabilizer and the weather stabilizer other than the hindered amine compound (Y) is, for example, 1% by mass or less, preferably 100% by mass or less, preferably 100% by mass. It is 0.5 mass% or less, More preferably, it is 0.3 mass% or less, Most preferably, it is 0.1 mass% or less.

  Examples of the heat stabilizer include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus Acids, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) pentaerythritol Phosphite heat stabilizers such as diphosphite; lactone heat stabilizers such as the reaction product 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] Hinders such as octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Examples include dophenol-based heat stabilizers, sulfur-based heat stabilizers, amine-based heat stabilizers, etc. In addition, these can be used singly or in combination of two or more. Stabilizers and hindered phenol heat stabilizers are preferred.

  As said weather resistance stabilizer, the 1 type (s) or 2 or more types of compound chosen from antioxidant, a ultraviolet absorber, etc. can be used.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, and the like.

  Examples of the phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t- Aryl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and other acrylates described in JP-A Nos. 63-179953 and 1-168643 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-tert-butylphenol), 4,4'-butylidene-bis (6-tert-butyl-m-crezo) ), 4,4′-thiobis (3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- ( 3-tert-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 [i.e. pentaerythrimethyl-tetrakis (3- (3,5-di- t Butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), tocophenol and the like alkyl-substituted phenol compounds; 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 Triazine group-containing phenolic compounds such as -4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine; Can be mentioned. Among these, acrylate-based phenol compounds and alkyl-substituted phenol compounds are preferable, and alkyl-substituted phenol compounds are particularly preferable.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, 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) ) Octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 10 Monophosphite compounds such as decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecylphos Phyto), 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-tridecyl phosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenedi Phosphite, cyclic neopentanetetrayl bis (isodecyl phosphite), cyclic neopentane tetrayl bis (nonylph) Nylphosphite), cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), cyclic neopentanetetra Examples thereof include diphosphite compounds such as irbis (2,6-di-t-butylphenyl phosphite). 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 antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thio. Dipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Is mentioned.

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

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a salicylic acid ultraviolet absorber, a benzotriazole ultraviolet absorber, an acrylate ultraviolet absorber, and a metal complex ultraviolet absorber.

  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 include dimethoxybenzophenone.

  Examples of the salicylic acid-based ultraviolet absorber include phenylsulcylate, 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 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 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-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2, 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] and the like.

  Examples of the acrylate ultraviolet absorber include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.

  As the metal complex salt ultraviolet absorber, a complex salt of nickel or cobalt is usually used. Specifically, nickel [2,2′thiobis (4-t-octyl) phenolate] normal butylamine, nickel dibutyldithiocarbamate, 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 hydrogenated rosin, disproportionated rosin, and polymerized rosin, and modified rosin esters thereof), terpene resins, terpene phenol resins, aromatic modifications. Examples include terpene resins, hydrogenated terpene resins, aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, alicyclic petroleum resins, hydrogenated petroleum resins, and alkylphenol resins.

  Examples of the plasticizer include tricresyl phosphate, trixyl phosphate, triphenyl phosphate, triethyl phenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, dicresyl monoxylenyl phosphate. , Arylalkyl phosphates, diphenylmonoxylenyl phosphates, morphophosphates, trioctyl phosphates, tris (isopropylphenyl) phosphates and other phosphate triester plasticizers; dimethyl phthalate, diethyl phthalate, phthalic acid Phthalic acids such as dibutyl, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, octyldecyl phthalate, butylbenzyl phthalate Stealth plasticizer; Fatty acid monobasic acid ester plasticizers such as butyl oleate and glycerol monooleate; Dibutyl adipate, di-n-fatty acid dibasic acid ester plasticizer; Dihydric alcohol ester plasticizer Agents; oxyester plasticizers and the like.

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, Calcium salt, sodium salt, magnesium salt, potassium salt, etc., aliphatic alcohols such as palmitic alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic 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 metal salts of fluoroalkylsulfonic acids.
Examples of the waxes include montan wax, peat wax, ozokerite ceresin wax, mineral wax such as petroleum wax, polyolefin wax such as polyethylene wax and polypropylene wax, Fischer-Tropsch wax, chemically modified hydrocarbon wax, substituted amide. Synthetic waxes such as wax, plant waxes, animal waxes and the like can be mentioned.
Examples of the oils include aromatic oils, naphthenic oils, mineral oils of paraffinic oils, natural and synthetic oils such as vegetable oils and silicone 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 (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4-30) (such as hydrogenated castor oil), glycol esters of fatty acids, Examples thereof include liquid paraffin.

  Examples of the nucleating agent include sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, [phosphoric acid-2,2′-methylenebis (4,6-di-t-butyl). Phenyl)] dihydroxyoxyaluminum, bis [phosphate-2,2′-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphate-2,2′-methylenebis (4,6 -Di-t-butylphenyl)] aluminum, sodium-bis (4-t-butylphenyl) phosphate, benzoic acid metal salts such as sodium benzoate, pt-butylaluminum benzoate, 1,3: 2,4 -Bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (O-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O-ethylbenzyl) Ridene) sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1, 3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol, 1,3-O- Examples include 3,4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,3: 2,4-bis (Op-chlorobenzylidene) sorbitol, and mixtures thereof.

  Examples of the friction wear improver include resin fillers such as ultrahigh molecular weight polyethylene filler, PTFE filler, and polyimide filler, and inorganic fillers such as boron nitride filler and aluminum nitride filler.

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

Examples of the phosphorus flame retardant include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, and tris (bromo). Halogen-containing phosphoric acid such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate Ester flame retardants; Aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyl di Phenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tri (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tri (trimethylphenyl) phosphate, tri ( Non-halogen phosphate ester flame retardants such as aromatic phosphates such as t-butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate; Aluminum phosphinate flame retardants such as aluminum dimethylphosphinate and aluminum diethylphosphinate Is mentioned.
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, phosphoric acid Guanidine, guanidine sulfate, guanidine sulfamate, guanidine tetraborate, guanidine carbonate, guanyl urea phosphate, guanyl urea sulfate, melamine, melamine melam melem, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polylin Examples include melamine acid, melam, melem, and melamine sulfate.
Examples of the antimony flame retardant include antimony oxide, antimony trioxide, antimony pentoxide, antimony tetroxide, and sodium antimonate.

  As the foaming agent, foaming agents generally used for foam molding of rubber can be widely used. Specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, etc. Inorganic foaming agent, nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexyl Azo compounds such as nitrile, azodiaminobenzene, barium azodicarboxylate, sulfonyl such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide Hydrazide compound Calcium azide, 4,4-diphenyl, di-sulfonyl azide, azide compounds such as p- toluenesulfonyl Le azide and the like.

  Examples of the antistatic agent and antifogging agent include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  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 heptadecane sulfonate, sodium octadecane sulfonate, sodium nonadecane sulfonate, sodium heicosan sulfonate, potassium decane sulfonate, potassium undecane sulfonate, potassium dodecane sulfonate, potassium tridecane sulfonate, tetradecane sulfonic acid Potassium, potassium pentadecanesulfonate, potassium hexadecanesulfonate, potassium heptadecanesulfonate, octadecanesulfone Alkyl sulfonates such as potassium acid, potassium nonadecane sulfonate, potassium heicosandecasulfonate, sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, tetra Examples include sodium decylbenzene sulfonate, sodium pentadecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, sodium heptadecyl benzene sulfonate, sodium octadecyl benzene sulfonate, alkyl benzene sulfonate, alkyl phosphate, and the like.

  Examples of the amphoteric surfactant include betaine compounds such as lauryl betaine, stearyl betaine, laurylamidopropyl betaine, stearylamidopropyl betaine, dimethylamine oxide compounds such as lauryl dimethylamine oxide and stearyl dimethylamine oxide, N-stearyl- Examples include alanine compounds such as α-alaninate and N-lauryl-α-alaninate.

  Examples of the nonionic surfactant include lauric acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride, caprylic acid monoglyceride, coconut fatty acid monoglyceride, lauric acid diglyceride, palmitic acid diglyceride, and stearic acid diglyceride. , Oleic acid diglyceride, behenic acid diglyceride, caprylic acid diglyceride, palm fatty acid diglyceride, lauric acid triglyceride, palmitic acid triglyceride, stearic acid triglyceride, oleic acid triglyceride, behenic acid triglyceride, caprylic acid triglyceride, coconut fatty acid triglyceride, pentaerythritol monolaurate , Bae Pentaerythritol fatty acid esters such as taerythritol monostearate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetralaurate, sorbitol monolaurate, sorbitol monostearate , Fatty acid esters of sorbitol, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol fatty acid esters such as polyethylene glycol distearate, fatty acid esters of polyhydric alcohols, lauric acid diethanolamide, stearic acid diethanolamine And palm fatty acid diethanolamide, etc. Diethanol amides.

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

  Examples of the anti-blocking agent include fine inorganic compounds such as silica, alumina, alumina silicate, and diatomaceous earth, and fine organic compounds such as polyethylene, crosslinked polyethylene, polymethyl methacrylate, and crosslinked polymethyl methacrylate.

  As said impact-resistant agent, various things, such as a (meth) acrylic ester ester impact-resistant agent which has a core-shell type structure, can be used, for example.

  Examples of the surface wetting improver include silane coupling agents such as vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. It is done.

Examples of the filler include inorganic fillers and organic fillers.
Examples of the inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice 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 derivatives thereof, cellulose and derivatives thereof, pulp and derivatives thereof, paper and derivatives thereof, flour, okara, bran, coconut shell, coffee cake, protein, phthalic acid, fat Group polybasic acid-based, glycerin-based, citric acid-based, glycol-based, and olefin-based low molecular weight materials, polyethylene terephthalate fiber, polyethylene naphthalate fiber, aramid fiber and the like.

  Examples of the hydrochloric acid absorbent 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 Examples include magnesium and zinc 12-hydroxystearate. Moreover, epoxy compounds such as epoxidized octyl stearate and epoxidized soybean oil; and inorganic compounds such as magnesium hydroxide, calcium hydroxide and hydrotalnite.

  Examples of the metal deactivator include N, N′-diphenyloxamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis ( 3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bis Examples thereof include phenyl hydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide, and the like.

[Method for Preparing Cyclic Olefin Copolymer Composition]
The preparation method of the cyclic olefin copolymer composition according to the present embodiment includes a cyclic olefin copolymer (m), a hindered amine compound (Y), and, if necessary, a cyclic olefin polymer (n ), An elastomer, and various additives. As a mixing method, a method of melt blending with an extruder or the like, or a suitable solvent such as a saturated hydrocarbon such as heptane, hexane, decane or cyclohexane; dissolved in an aromatic hydrocarbon such as toluene, benzene or xylene, A solution blending method performed by dispersing can be employed.

[varnish]
The cyclic olefin copolymer composition according to this embodiment can be made into a varnish by mixing with a solvent.
The solvent for preparing the varnish is not particularly limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (m) and the hindered amine compound (Y). What is preferably used as the solvent is, for example, saturated hydrocarbons such as heptane, hexane, octane, decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decahydronaphthalene; aroma such as toluene, benzene, xylene, mesitylene, pseudocumene Group hydrocarbons; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; methyl Cellsolves such as cellsolve and ethylcellsolve; Esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; Ethylene, dichloroethylene, halogenated hydrocarbons such as chlorobenzene are used. Preferably heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene are used. These solvents can be used alone or in admixture of two or more at any ratio.

In the present embodiment, the method for producing the varnish may be carried out by any method, but usually includes a step of mixing the cyclic olefin copolymer composition and the solvent. About mixing of each component, there is no restriction | limiting in the order. There is no restriction | limiting as an apparatus which prepares a varnish, You may implement by what kind of apparatus of a batch type or a continuous type which can be stirred and mixed. The temperature for preparing the varnish can be arbitrarily selected in the range from room temperature to the boiling point of the solvent.
In addition, you may prepare a varnish by using the reaction solution at the time of obtaining a cyclic olefin type copolymer (m) as a solvent as it is, and dissolving a hindered amine type compound (Y) there. Moreover, you may prepare a varnish by mixing the varnish of the hindered amine type compound (Y) prepared separately with the reaction solution at the time of the cyclic olefin type copolymer (m) being obtained.

[Method for producing crosslinked body (Q)]
The crosslinked body (Q) is a crosslinked body of the cyclic olefin copolymer composition according to the present embodiment, and crosslinks the cyclic olefin copolymer (m) in the above cyclic olefin copolymer composition. Can be obtained. Although there is no restriction | limiting in particular as a crosslinking method of a cyclic olefin type copolymer (m), While shape | molding in arbitrary forms using a radical polymerization initiator, sulfur, a hydrosilyl group containing compound, an electron beam, and other radiation, Or the method of bridge | crosslinking after shaping | molding etc. are mentioned.

  For crosslinking with a radical polymerization initiator, the usual crosslinking method with a radical polymerization initiator applied to polyolefins can be applied as it is. That is, a radical polymerization initiator such as dicumyl peroxide is blended in the cyclic olefin copolymer composition, and heated and crosslinked. Although the mixing 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 per 100 parts by mass of the cyclic olefin copolymer (m). Preferably it is 0.5-10 mass parts. When the blending ratio of the radical polymerization initiator is not more than the above upper limit value, the dielectric properties of the crosslinked product (Q) are improved, and when it is more than the above lower limit value, the heat resistance and mechanical properties of the crosslinked product (Q) are improved. Can be made.

  As said radical polymerization initiator, a well-known thermal radical polymerization initiator, radical photopolymerization initiator, and these can be used together. Among these radical polymerization initiators, when a thermal radical polymerization initiator is used, the 10-hour half-life temperature is usually 80 ° C. or higher, preferably 120 ° C. or higher, from the viewpoint of storage stability. Examples of such initiators include dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis (t-butylperoxy) 2,5-dimethylhexane, 2,5-bis (t-butylperoxide). Dialkyl peroxides such as oxy) 2,5-dimethylhexyne-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, , 6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane and the like; bis (t-butylperoxy) isophthalate, t-butylperoxybenzoate, t- Peroxyesters such as butylperoxyacetate; t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide Hydroperoxides such as p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4- Trioxepan etc. are mentioned.

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

In the case of crosslinking with sulfur or the like, the cyclic olefin copolymer composition is mixed with a sulfur-based compound, and if necessary, a vulcanization accelerator and a vulcanization acceleration assistant, and heated to carry out a crosslinking reaction. Although there is no restriction | limiting in particular in the compounding quantity of a sulfur type compound, Cyclic olefin type copolymer (m) 100 mass from the surface of making a crosslinking reaction progress efficiently and measuring the physical property improvement of the obtained crosslinked material, and economical efficiency. The amount is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, and usually 0.1 to 20 when used together with a vulcanization accelerator or vulcanization accelerator. It is used in the range of parts by mass, preferably 0.2 to 10 parts by mass.
Various known sulfur compounds can be used for causing the crosslinking reaction. For example, sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate Etc. Various vulcanization accelerators can be used, such as N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N-diisopropyl-2-benzothiazole. Thiazoles such as sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, benzothiazyl-disulfide; Guanidines such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, orthosolyl biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant; butyraldehyde-aniline condensate; hexamethylenetetra Aldehyde amines such as ammonia, acetaldehyde ammonia, or aldehyde-ammonia; imidazolines such as 2-mercaptoimidazoline; thioureas such as thiocarbanilide, diethylthioureadibutylthiourea, trimethylthiourea, diorthorthrylthiourea; tetramethylthiuram Thiurams such as monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, ethylphenyl Zinc dithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, dimethyl Le dithiocarbamate selenium, dithio acid salt-based tellurium diethyldithiocarbamate and the like; dibutyl xanthate acid zinc xanthate system; and the like. Vulcanization accelerators include zinc oxide, activated zinc white, zinc carbonate, composite zinc white, magnesium oxide, lisage, red lead, basic lead carbonate and other metal oxides, stearic acid, oleic acid, lauric acid, Examples include fatty acid type such as lead stearate, organic amine / glycol type such as triethanolamine and diethylene glycol.

  The temperature for crosslinking the cyclic olefin copolymer composition for both radical polymerization initiator crosslinking and sulfur crosslinking is usually 100 to 300 ° C, preferably 120 to 250 ° C, more preferably 120 to 220 ° C. Cross-linking may be performed by changing in stages. When it is at least the lower limit, crosslinking can be sufficiently advanced. Moreover, coloring below the said upper limit can suppress coloring of the crosslinked body obtained, or can simplify a process. For reference, polybutadiene, which is a typical double bond-containing polymer, generally cannot be crosslinked under the above conditions, and requires crosslinking conditions at a high temperature such as 300 ° C.

  The cyclic olefin copolymer composition according to the present embodiment can be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule. About the bridge | crosslinking using a hydrosilyl group containing compound, it can carry out according to the method of Unexamined-Japanese-Patent No. 2015-193680, for example. Details are omitted here.

  The method of crosslinking using an electron beam or other radiation has the advantage that it is not accompanied by restrictions on temperature and fluidity during molding, and examples of radiation include γ rays, UV, etc. in addition to electron beams. .

  In any case of a method using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, or the like, or a method of crosslinking using radiation, crosslinking can be carried out in combination with a crosslinking aid.

  The crosslinking aid is not particularly limited, but for example, oximes such as p-quinone dioxime, p, p′-dibenzoylquinone dioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl Methacrylates, acrylic acid / zinc oxide mixtures, acrylates or methacrylates such as allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; hexamethylene diallyl nadiimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl Allyl compounds such as monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate; N, N′-m-phenylenebismaleimide, N N '- (4,4'-methylene diphenylene) maleimide compounds such dimaleimide like, vinyl norbornene, ethylidene norbornene, cyclic non-conjugated dienes such as dicyclopentadiene. These crosslinking aids may be used alone or in combination.

  The crosslinking reaction can be carried out in a molten state with a mixture of the cyclic olefin copolymer composition and the above-mentioned radical polymerization initiator, sulfur, hydrosilyl group-containing compound or the like, or the mixture is dissolved in a solvent. Alternatively, it can be carried out in a dispersed solution state, or the solvent can be volatilized from a solution state dissolved in a solvent and formed into an arbitrary shape such as a film or a coating, and the crosslinking reaction can be further advanced.

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

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

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

[Film or sheet]
The crosslinked product of the cyclic olefin copolymer composition according to this embodiment can be formed into a film or a sheet and used for various applications. As a method for forming a film or a sheet using the cyclic olefin copolymer composition according to this embodiment, various known methods can be applied. For example, a method may be mentioned in which the varnish described above is applied onto a supporting substrate such as a thermoplastic resin film, dried, and then subjected to heat treatment to form a cyclic olefin copolymer composition by crosslinking. Although the coating method to the support base material of a varnish is not specifically limited, For example, the application | coating using a spin coater, the application | coating using a spray coater, the application | coating using a bar coater etc. can be mentioned.
Moreover, the method of melt-molding the cyclic olefin type copolymer composition which concerns on this embodiment, and obtaining a film or a sheet | seat can also be mentioned.

[Laminate]
The film or sheet according to the present embodiment can be used for various applications as a laminate by laminating on a substrate. Various known methods can be applied to the method of forming the laminate according to the present embodiment.
For example, a laminated body can be produced by laminating a film or sheet produced by the above-described method on a substrate and heat-curing with a press or the like as necessary.
Moreover, a laminated body can also be manufactured by laminating | stacking the electrically insulating layer containing the crosslinked body mentioned above with respect to a conductor layer.

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

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

Inorganic and / or organic fibers can be used as the fibers constituting the sheet-like fiber substrate according to the present embodiment, and are not particularly limited. For example, PET (polyethylene terephthalate) fibers, aramid fibers, and ultra-high molecular polyethylene 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 And the like. 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, and T glass.
The impregnation of the sheet-like fiber base material with the varnish is performed, for example, by dipping and coating. The impregnation may be repeated a plurality of times as necessary.
These sheet-like fiber base materials can be used alone or in combination of two or more, and the amount used is appropriately selected as desired, but usually 10 to 90 mass in the prepreg or laminate. %, Preferably 20 to 80% by mass, more preferably 30 to 70% by mass. Within this range, the dielectric properties and mechanical strength of the resulting laminate are highly balanced, which is preferable.

  Although the thickness of the prepreg which concerns on this embodiment is suitably selected according to a use purpose, Usually, it is 0.001-10 mm, Preferably it is 0.005-1 mm, More preferably, it is 0.01-0. 5 mm. If it exists in this range, the characteristics, such as the shaping property at the time of lamination | stacking, and the mechanical strength of a laminated body obtained by hardening, and toughness, are fully exhibited and are suitable.

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

Since the metal-clad laminate according to the present embodiment uses the cyclic olefin copolymer composition according to the present embodiment, the metal-clad laminate is excellent in heat aging resistance while satisfying dielectric properties suitable for a printed wiring board. ing.
Therefore, the metal-clad laminate according to this embodiment can be suitably used as an insulating layer material for a printed wiring board.

[Printed wiring board]
The cyclic olefin copolymer composition according to this embodiment is excellent in dielectric properties, heat resistance, mechanical properties, and the like, and therefore can be suitably used for printed wiring boards.
A generally known method can be adopted as a method for producing a printed wiring board, and is not particularly limited. Form. Next, a conductor layer is laminated on the obtained electrical insulating layer by a known method to produce a laminate. Then, a printed wiring board can be obtained by carrying out circuit processing etc. of the conductor layer in this laminated body.

  As a metal used as a conductor layer, metals, such as copper, aluminum, nickel, gold | metal | money, silver, stainless steel, can be used. As a method for forming the conductor layer, for example, a method in which the metal is heat-sealed on the electrical insulating layer as a foil, or a method in which the metal is foil-bonded to the electrical insulating layer using an adhesive Or a method of forming a conductor layer made of the metal on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating. As an aspect of the printed wiring board, either a single-sided board or a double-sided board may be used.

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

[Foam]
Moreover, it can be set as a foam by bridge | crosslinking and foaming the cyclic olefin type copolymer composition which concerns on this embodiment. At this time, the foaming agent described above may be added to the cyclic olefin copolymer composition.

[Usage]
Since the cyclic olefin copolymer composition and the crosslinked product (Q) according to the present embodiment are excellent in solvent resistance, heat resistance, mechanical strength, and transparency, a molded product composed of the crosslinked product is, for example, an optical fiber, Optical waveguide, optical disk substrate, optical filter, lens, optical adhesive, optical filter for PDP, coating material for organic EL, base film substrate for solar cell in aerospace field, coating material for solar cell and thermal control system, semiconductor Overcoat materials such as devices, light emitting diodes, electronic devices such as various memories, hybrid ICs, MCMs, printed wiring boards, printed wiring boards, and prepregs and laminates, display components, etc. or interlayer insulation Materials, substrates for liquid crystal displays and solar cells, medical instruments, automotive components, release agents, resin modifications Agent, transparent substrate for display, lithium ion battery member, semiconductor process member, film capacitor, gas barrier coating material, wire clothing material, automotive member, aerospace member, semiconductor process material, wire coating material, for lithium ion battery Member, fuel cell member, capacitor film, flexible display member, anchor coat material, transparent adhesive, modifier, cross-linking aid, medical container, medical catheter member, waterproof seal material, release material, hard coat material, It can be used in applications such as foam modifiers.
In particular, it has excellent dielectric property stability over time and is excellent in solvent resistance, heat resistance, transparency, mechanical properties, etc., and therefore can be suitably used for high-frequency applications such as a high-frequency circuit board. Furthermore, since it has excellent gas barrier properties, it can be suitably used as a substrate, film or sheet for liquid crystal displays and solar cells.

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

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

  In addition, the composition and intrinsic viscosity [η] of the cyclic olefin copolymer (m) used in Synthesis Examples, Examples, and Comparative Examples were measured by the following methods.

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

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

  The films and laminates obtained in Examples and Comparative Examples were evaluated by the following method.

Dielectric loss tangent evaluation: The dielectric loss tangent at 10 GHz was evaluated by the cylindrical cavity resonator method for the single-layer films obtained in Examples and Comparative Examples. Here, the single layer film was subjected to heat treatment at 125 ° C. for 485 hours, the dielectric loss tangent before and after the heat treatment was measured, and the heat aging resistance of the film was evaluated based on the amount of change in dielectric loss tangent before and after the heat treatment.
Dielectric loss tangent evaluation: With respect to the laminates obtained in the examples and comparative examples, the dielectric loss tangent at 12 GHz was evaluated by the cylindrical cavity resonator method. Here, the laminate is subjected to heat treatment at 125 ° C. for 100 to 1000 hours, and the dielectric loss tangent is measured before, 100 hours, 200 hours, and 1000 hours before the heat treatment, and the amount of change in the dielectric loss tangent before and after the heat treatment. Thus, the heat aging resistance of the laminate was evaluated.

Oxidation degradation degree evaluation: About the monolayer film obtained by the Example and the comparative example, the transmission spectrum of the film was measured using the Fourier-transform infrared spectrophotometer (FT-IR). A 1710～1720Cm ^-1 vicinity of C = O bonds by absorption intensity (I (C = O)) , the ratio of the intensity of the absorption by C-H bond around wave number ^{1460cm -1 (I (C-H} )) (I (C = O) / I (C−H)) was used as an index of the degree of oxidative deterioration. Here, the single layer film was subjected to heat treatment at 125 ° C. for 485 hours, and I (C═O) / I (C—H) before and after the heat treatment were measured, and I (C═O) before and after the heat treatment. The heat aging resistance of the film was evaluated by the amount of change in / I (C—H).

  The following raw materials were used for the experiment.

Transition metal compound (1)
(Synthesis by the method described in JP 2004-331965 A.)

MMAO (manufactured by Tosoh Finechem)
Toluene (Wako Pure Chemical Industries, Ltd .: Wako Special Grade)
Xylene (Wako Pure Chemical Industries, Ltd .: Wako Special Grade)
5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (Mitsui Chemicals, Inc.)
Acetone (Wako Pure Chemical Industries, Ltd .: Wako Special Grade)
Methanol (Wako Pure Chemical Industries, Ltd .: Wako Special Grade)

Cyclic olefin polymer (n):
Polymer 1: Ethylene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene (Product name: Apel 6509T, manufactured by Mitsui Chemicals)

Hindered amine compound (Y):
Compound (Y) -1: CHIMASSORB 944 FDL (molecular weight 2000-3100) (manufactured by BASF)
Compound (Y) -2: CHIMASSORB 2020 FDL (molecular weight 2600-3400) (manufactured by BASF)
Compound (Y) -3: LA-52 (molecular weight 847) (manufactured by ADEKA)
Compound (Y) -4: TINUVIN 770DF (molecular weight 481) (manufactured by BASF)

Hindered phenol compound (X):
Compound (X) -1: Irganox 1010 (manufactured by BASF)
Compound (X) -2: Irganox 1076 (manufactured by BASF)

Radical polymerization initiator:
Crosslinking agent 1: Park Mill D (Nippon Yushi Co., Ltd.)

[Synthesis Example 1]
A SUS autoclave with an internal volume of 4 L that was sufficiently purged with nitrogen was charged with 1670 ml of xylene, 212 ml of 5-vinyl-2-norbornene (VNB), tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene (TD) 120 ml, MMAO (manufactured by Tosoh Finechem Co.) in toluene, 4 mmol in terms of Al, and hydrogen 1984 ml are added, until ethylene reaches a total pressure of 0.6 MPa. Introduced. 0.04 mmol of the transition metal compound (1) was dissolved in 10 ml of toluene and added to initiate polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 25 ° C. for 60 minutes, and then the polymerization was stopped by injecting 5 ml of methanol. After completion of the polymerization, the reaction product was put into a mixed solvent of 15 L of acetone and 5 L of methanol to which 20 ml of concentrated hydrochloric acid had been added to precipitate the whole amount of the polymer. After stirring, the reaction product was filtered through a filter paper. This operation was repeated until the reaction product disappeared, and the entire polymer obtained was dried under reduced pressure at 80 ° C. for 10 hours to obtain 261 g of an ethylene / TD / VNB copolymer. The intrinsic viscosity [η] was 0.40 (dL / g), the composition ratio of the VNB-derived structure in the polymer determined by NMR was 25.7 mol%, and the composition ratio of the TD-derived structure was 10.6 mol%. The glass transition temperature measured by DSC was 101 ° C.

[Example 1]
(Preparation of varnish 1)
The cyclic olefin copolymer (m) obtained in Synthesis Example 1, the polymer 1 as the cyclic olefin polymer (n), the crosslinking agent 1 as the radical polymerization initiator, and the compound (as the hindered amine compound (Y)) Y) -1, xylene was used as a solvent, and weighed according to the composition of Table 1. The weighed sample was stirred until it was sufficiently dissolved to obtain the intended varnish-like cyclic olefin copolymer composition. In Tables 1 and 2, the unit of the mixing ratio of each raw material is part by mass.

(Film casting)
The obtained varnish-like cyclic olefin copolymer composition was coated on a PET film at a speed of 10 mm / second, and then dried in a blower dryer at 110 ° C. for 2 minutes and at 170 ° C. for 2 minutes in a nitrogen stream. did. Subsequently, it heated up at 180 degreeC and heated for 1 hour, and obtained the 40-micrometer-thick single layer film which consists of a crosslinked body. The obtained film was peeled off from the PET film and evaluated. The obtained results are shown in Table 1.

[Comparative Example 1]
Except having changed into the compounding composition shown in Table 1, the film was produced similarly to Example 1 and evaluation was implemented. That is, a film was prepared without adding the hindered amine compound (Y), and evaluation was performed in the same manner as in Example 1.

[Examples 2 and 3]
Except having changed into the compounding composition shown in Table 1, the film was produced similarly to Example 1, and each evaluated. The obtained results are shown in Table 1.

[Comparative Examples 2 and 3]
Except having changed into the compounding composition shown in Table 1, the film was produced similarly to Example 1, and each evaluated. The obtained results are shown in Table 1.

[Example 4]
The cyclic olefin copolymer (m) obtained in Synthesis Example 1, the polymer 1 as the cyclic olefin polymer (n), the crosslinking agent 1 as the radical polymerization initiator, and the compound (as the hindered amine compound (Y)) Y) -1, xylene was used as a solvent, and weighed according to the composition shown in Table 2. The weighed sample was stirred until it was sufficiently dissolved to obtain the desired varnish-like cyclic olefin copolymer composition.

(Film casting)
The obtained varnish-like cyclic olefin copolymer composition was coated on a PET film at a speed of 10 mm / second, and then dried in a blower dryer at 110 ° C. for 2 minutes and at 170 ° C. for 2 minutes in a nitrogen stream. did. Subsequently, it heated up at 180 degreeC and heated for 1 hour, and the film 1 with a thickness of 15 micrometers which consists of a crosslinked body was obtained.

(Preparation of laminate 1)
A laminate 1 having a thickness of 0.8 mm was produced by stacking 60 pieces of the film 1 in a 150 mm square and heating it with a vacuum press machine at a pressure of 3.5 MPa and 200 ° C. for 2 hours. The dielectric loss tangent measurement of the obtained laminated body 1 was performed. The obtained results are shown in Table 2.

[Examples 5 and 6]
Except having changed into the composition shown in Table 2, each laminated body was produced similarly to Example 4, and evaluation was implemented, respectively. The obtained results are shown in Table 2.

[Comparative Example 4]
Except having changed into the composition shown in Table 2, the laminated body was produced similarly to Example 4 and evaluated. The obtained results are shown in Table 2.

Claims (13)

A cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and a hindered amine compound (Y) having a piperidyl group represented by the following general formula (1):
The cyclic olefin copolymer (m) is:
(A) a repeating unit derived from one or more olefins represented by the following general formula (I);
(B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III):
(C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V),
When the total number of repeating units in the cyclic olefin copolymer (m) is 100 mol%, the content of the repeating unit (A) derived from the olefin is 10 mol% or more and 90 mol% or less, The content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 30 mol% or less,
When the content of the cyclic olefin copolymer (m) contained in the cyclic olefin copolymer composition is 100 parts by mass, the hindered amine compound in the cyclic olefin copolymer composition. The cyclic olefin copolymer composition whose content of (Y) is 0.01 mass part or more and 5 mass parts or less.

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

[In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. A monocyclic ring or a polycyclic ring may be formed. ]

[In the general formula (V), 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. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 aromatic hydrocarbon groups, R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. ]

[In the general formula (1), X is a hydrogen atom, an oxy radical group, an alkyl group, an alkoxy group, an aryl group, or a hydroxy group, and R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom. Or an alkyl group. ] The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene is 5-vinyl-2-norbornene or 8-vinyl-9-methyltetracyclo [4.4.0.1 ^2,5 . The cyclic olefin copolymer composition according to claim 1, which is 1 ^7,10 ] -3-dodecene. The cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin is bicyclo [2.2.1] -2-heptene or tetracyclo [4.4.0.1 ^2,5 . The cyclic olefin copolymer composition according to claim 1, which is 1 ^7,10 ] -3-dodecene. A cyclic olefin polymer (n) different from the cyclic olefin copolymer (m);
The cyclic olefin polymer (n) is a copolymer (n1) of ethylene or an α-olefin and a cyclic olefin (wherein the copolymer (n1) is a cyclic non-polymer represented by the following general formula (III): Including no repeating unit derived from a conjugated diene) and a ring-opening polymer of cyclic olefin (n2),
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) is 100% by mass,
The content of the cyclic olefin polymer (m) is 5% by mass or more and 95% by mass or less, and the content of the cyclic olefin polymer (n) is 5% by mass or more and 95% by mass or less. The cyclic olefin type copolymer composition as described in any one of thru | or 3.

[In the general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 are the same as each other. It may be different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ⁷⁵ and R ⁷⁶ are bonded to each other. A monocyclic ring or a polycyclic ring may be formed. ]   The cyclic olefin copolymer composition according to any one of claims 1 to 4, wherein the hindered amine compound (Y) has a molecular weight of 1000 or more.   A varnish containing the cyclic olefin copolymer composition according to any one of claims 1 to 5 and a solvent.   A crosslinked product of the cyclic olefin copolymer composition according to any one of claims 1 to 5.   A film or sheet comprising the crosslinked product according to claim 7.   The laminated body which laminated | stacked the film or sheet of Claim 8 on the base material.   A prepreg comprising the cyclic olefin copolymer composition according to any one of claims 1 to 5 and a sheet-like fiber base material.   A metal-clad laminate obtained by laminating at least one selected from the film or sheet according to claim 8, the laminate according to claim 9, and the prepreg according to claim 10 and a metal foil.   An electrical insulating layer formed of at least one selected from the film or sheet according to claim 8, the laminate according to claim 9, and the prepreg according to claim 10, and provided on the electrical insulating layer. Printed circuit board comprising a conductive layer.   An electronic apparatus comprising the printed wiring board according to claim 12.