JP2019081898A - Cyclic olefinic copolymer, cyclic olefinic copolymer composition and crosslinked body - Google Patents

Abstract

To provide a cyclic olefinic copolymer that makes it possible to obtain a crosslinked body having excellent dielectric properties in a high frequency region suitable for a circuit board or the like, and also has excellent moldability, and a cyclic olefinic copolymer composition.SOLUTION: A cyclic olefinic copolymer (m) has a crosslinkable group, containing (A) a repeating unit derived from at least one olefin represented by a specific chemical formula, (B) a repeating unit derived from at least one cyclic nonconjugated diene represented by a specific chemical formula, and (C) a repeating unit derived from at least one cyclic olefin represented by a specific chemical formula. The content of the (B) cyclic nonconjugated diene-derived repeating unit is 19 mol% or more and 36 mol% or less, and the number average molecular weight Mn is 3,000 or more and 16,000 or less.SELECTED DRAWING: None

Description

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

  Recently, in addition to the increase in wireless communication devices and the like that use high frequency bands, with the increase in communication speed, frequency bands in high bands have inevitably been used in many cases. Along with this, in order to reduce transmission loss at high frequency to the limit, a circuit board having a small dielectric loss tangent is required.

  As a resin material used for such a circuit board, the cyclic olefin system copolymer which copolymerized the diene described in patent documents 1 and patent documents 2 is mentioned, for example.

Patent Document 1 and Patent Document 2 disclose that a sheet obtained by crosslinking a cyclic olefin-based copolymer obtained by copolymerizing a specific diene compound with an organic peroxide or the like exhibits excellent dielectric properties. There is.
Patent Document 3 discloses a crosslinkable resin molded article having excellent fluidity at the time of heating for a crosslinkable resin molded article containing a crosslinkable cycloolefin polymer.

JP, 2010-100843, A International Publication No. 2012/046443 JP, 2016-190987, A

According to the study of the present inventors, cyclic olefin copolymers having a crosslinkable group as described in Patent Document 1 and Patent Document 2 have a high glass transition temperature and a crosslinked product having excellent heat resistance is obtained. However, it has become clear that the flowability during heating tends to be poor. Therefore, the melt viscosity of the resin composition containing the cyclic olefin copolymer becomes high, sufficient fluidity can not be obtained, and it is impossible to sufficiently suppress the impregnation failure to the fiber base material and the wiring embedding failure at the time of circuit board production. It became clear that there was a tendency.
Further, it has become clear that, although the crosslinkable resin molded product containing the crosslinkable cycloolefin polymer described in Patent Document 3 has good flowability, sufficient heat resistance and mechanical strength tend not to be obtained. The
From the above, the cyclic olefin copolymer having a crosslinkable group has room for improvement in terms of improving the formability while maintaining the excellent dielectric properties of the cyclic olefin copolymer.

  The present invention has been made in view of the above circumstances, and it is possible to obtain a crosslinked product having excellent dielectric properties in a high frequency region suitable for a circuit board or the like, and also to obtain a cyclic olefin-based copolymer having excellent formability. It is intended to provide a coalescent and cyclic olefin copolymer composition.

  As a result of intensive studies to solve the above problems, the present inventors can obtain the circuit substrate by adjusting the number average molecular weight Mn of the cyclic olefin copolymer obtained by copolymerizing a specific diene compound to a specific range. The inventors have found that a cyclic olefin copolymer having good formability can be obtained while satisfying dielectric properties in a high frequency region, and the present invention has been completed.

  That is, according to the present invention, the following cyclic olefin copolymer, cyclic olefin copolymer composition and crosslinked product are provided.

〔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。〕
［２］
上記［１］に記載の環状オレフィン系共重合体において、
上記環状オレフィン系共重合体中の繰り返し単位の合計モル数を１００モル％とした場合に、上記環状非共役ジエン由来の繰り返し単位（Ｂ）の含有量と上記環状オレフィン由来の繰り返し単位（Ｃ）の含有量の合計が４０モル％未満の範囲である環状オレフィン系共重合体。
［３］
上記［２］に記載の環状オレフィン系共重合体において、
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−ノルボルネンを含み、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テトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセンを含む環状オレフィン系共重合体。
［４］
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（ｍ）を含む環状オレフィン系共重合体組成物。
［５］
上記［４］に記載の環状オレフィン系共重合体組成物において、
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）は上記一般式（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％以下である環状オレフィン系共重合体組成物。
［６］
上記［４］または［５］に記載の環状オレフィン系共重合体組成物から選択される少なくとも一種と、溶媒と、を含有するワニス。
［７］
上記［４］または［５］に記載の環状オレフィン系共重合体組成物を架橋して得られる架橋体。
［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［７］に記載の架橋体を含む電気絶縁層と、上記電気絶縁層上に設けられた導体層とを含む回路基板。
［１１］
上記［１０］に記載の回路基板を備えた電子機器。
［１２］
上記［４］または［５］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。 [1]
(A) One or more olefin-derived repeating units represented by the following general formula (I):
(B) Repeating units derived from one or more cyclic non-conjugated dienes represented by the following general formula (III):
(C) A cyclic olefin-based copolymer (m) containing one or more cyclic olefin-derived repeating units represented by the following general formula (V),
When the total number of moles of the repeating units in the cyclic olefin copolymer is 100 mol%,
The content of the repeating unit (B) derived from the above cyclic non-conjugated diene is 19 mol% or more and 36 mol% or less,
The number average molecular weight Mn of the cyclic olefin copolymer is in the range of 3,000 to 16,000,
Cyclic olefin copolymer having a crosslinkable group.

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

[In the above general formula (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 identical to each other It may be different, and 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 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 It may form a single ring or multiple rings. ]

[In the above 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 identical to each other It may be different, and 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 And R ^{75 to} R ⁷⁸ may be bonded to each other to form a single ring or multiple rings. ]
[2]
In the cyclic olefin-based copolymer described in the above [1],
When the total number of moles of the repeating units in the cyclic olefin copolymer is 100 mol%, the content of the repeating unit (B) derived from the cyclic non-conjugated diene and the repeating unit (C) derived from the cyclic olefin Cyclic olefin-based copolymer whose total content is less than 40 mol%.
[3]
In the cyclic olefin copolymer as described in the above [2],
The cyclic nonconjugated diene constituting the repeating unit (B) derived from the cyclic nonconjugated diene contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin is tetracyclo [4. 4.0.1 ^2,5 . The cyclic olefin type copolymer containing ^1,7,10 ] -3- dodecene.
[4]
A cyclic olefin copolymer composition comprising the cyclic olefin copolymer (m) according to any one of the above [1] to [3].
[5]
In the cyclic olefin copolymer composition according to the above [4],
It further contains a cyclic olefin polymer (n) different from the above cyclic olefin copolymer (m),
The cyclic olefin polymer (n) is a copolymer of ethylene or an α-olefin and a cyclic olefin (n1) (however, the copolymer (n1) is a cyclic non-polymer represented by the general formula (III)) Containing at least one selected from conjugated diene-based repeating units) and a ring-opened polymer of cyclic olefin (n2),
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) is 100 mass%,
Content of the said cyclic olefin type copolymer (m) is 5 mass% or more and 95 mass% or less, Content of cyclic olefin type polymer (n) is 5 mass% or more and 95 mass% or less cyclic olefin Copolymer composition.
[6]
A varnish containing at least one selected from the cyclic olefin copolymer composition according to the above [4] or [5], and a solvent.
[7]
The crosslinked body obtained by bridge | crosslinking the cyclic olefin type copolymer composition as described in said [4] or [5].
[8]
The film or sheet containing the crosslinked body as described in said [7].
[9]
The laminated body which laminated | stacked the film or sheet as described in said [8] on a base material.
[10]
The circuit board containing the electric-insulation layer containing the bridge | crosslinking body as described in said [7], and the conductor layer provided on the said electric-insulation layer.
[11]
The electronic device provided with the circuit board as described in said [10].
[12]
The prepreg containing the cyclic olefin type copolymer composition as described in said [4] or [5], and a sheet-like fiber base material.

  According to the present invention, it is possible to obtain a crosslinked product having excellent dielectric properties in a high frequency region suitable for circuit boards and the like, and a cyclic olefin-based copolymer and cyclic olefin-based copolymer excellent in moldability. A composition can be provided.

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

[Cyclic olefin copolymer (m)]
First, the cyclic olefin copolymer (m) of the embodiment according to the present invention will be described.
The cyclic olefin-based copolymer (m) according to the present embodiment includes (A) a repeating unit derived from one or more olefins represented by the following general formula (I), and A cyclic group having a crosslinkable group containing a repeating unit derived from one or more cyclic non-conjugated dienes and a repeating unit derived from one or more cyclic olefins (C) It is an olefin copolymer.

And, the content of the repeating unit (B) derived from cyclic non-conjugated diene is 19 mol% or more and 36 mol% or less, preferably 20 mol% or more and 33 mol% or less, more preferably 23 mol% or more and 30 mol% or less .
The crosslinked body (Q) obtained from the cyclic olefin copolymer (m) is excellent in the temporal stability of the dielectric characteristics when the content of the repeating unit (B) derived from the cyclic nonconjugated diene is within the above range It is also excellent in 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 body excellent in the balance of these physical properties can be obtained.
When the content of the repeating unit (B) derived from the cyclic non-conjugated diene is not more than the above upper limit, the formability and solubility of the cyclic olefin copolymer (m) are improved, and the dielectric properties of the crosslinked product (Q) Stability over time is improved. The heat resistance and mechanical properties of the crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer (m) when the content of the repeating unit (B) derived from the cyclic nonconjugated diene is not less than the above lower limit value The characteristics are improved.

Further, the number average molecular weight Mn of the cyclic olefin copolymer (m) is 3,000 or more, preferably 4,500 or more, more preferably 6,000 or more. Crosslinking the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment that the number average molecular weight Mn of the cyclic olefin copolymer (m) is not less than the above lower limit value The dielectric properties, heat resistance and mechanical properties of the crosslinked product (Q) obtained by
Further, the number average molecular weight Mn of the cyclic olefin copolymer (m) is 16,000 or less, preferably 14,500 or less, more preferably 13,000 or less. Circuit board preparation of the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment that the number average molecular weight Mn of the cyclic olefin copolymer (m) is not more than the above upper limit value It is possible to improve the formability such as the impregnating ability to the fiber base material at the time and the wire embedding property.
The number average molecular weight Mn of the cyclic olefin copolymer (m) can be controlled by polymerization conditions such as a polymerization catalyst, cocatalyst, H ₂ addition amount, polymerization temperature and the like.

Here, when the number average molecular weight Mn of the cyclic olefin copolymer (m) is within the above range, it has excellent dielectric properties possessed by the cyclic olefin copolymer (m) while having fluidity and mechanical properties. And, the formability such as the impregnating ability to the fiber base material at the time of circuit board production and the wiring embedding property can be improved.
Here, in the conventional cyclic olefin copolymer, when the weight average molecular weight is in the above range, the molecular weight is relatively low, so the heat resistance, dielectric properties, mechanical properties, etc. of the resulting crosslinked product are obtained. It tends to decline. However, the cyclic olefin copolymer (m) according to the present embodiment has good impregnatability to the fiber base even when the number average molecular weight Mn is within the above range, and addition of an inorganic filler, a flame retardant, etc. Since the mixing property with the agent is improved, the decrease in mechanical strength can be suppressed.

In the cyclic olefin copolymer (m) according to the present embodiment, when the total number of moles of the repeating units in the cyclic olefin copolymer (m) is 100 mol%, the cyclic unit derived from the cyclic non-conjugated diene The sum of the content of (B) and the content of the repeating unit (C) derived from cyclic olefin is preferably in the range of less than 40 mol%, more preferably in the range of less than 38 mol%, still more preferably 37 It is in the range of less than mol%.
The lower limit of the sum of the content of the repeating unit (B) derived from the cyclic non-conjugated diene and the content of the repeating unit (C) derived from the cyclic olefin is not particularly limited, but for example 20 mol% or more, preferably 26 mol% is there.

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

In the above general formula (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 as or different from each other, and 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 R 3 is 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 And R ⁷⁵ and R ⁷⁶ may be combined with each other to form a single ring or multiple rings.

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

In the cyclic olefin copolymer (m), when the total number of moles of the repeating units in the cyclic olefin copolymer (m) is 100 mol%, the content of the repeating unit (A) derived from an olefin is preferable Is preferably 20 to 80 mol%, more preferably 30 to 75 mol%, still more preferably 40 to 70 mol%, particularly preferably 50 to 70 mol%. The content of the repeating unit (B) derived from a conjugated diene is 19 mol% or more and 36 mol% or less, preferably 20 mol% or more and 33 mol% or less, more preferably 23 mol% or more and 30 mol% or less The content of the repeating unit (C) is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, still more preferably 7 Or Le% 20 mol% or less.
The crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has the temporal stability of dielectric characteristics when the content of each repeating unit in the cyclic olefin copolymer (m) is within the above range. It is excellent in heat resistance as well as excellent in properties. 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) excellent in the balance of these physical properties can be obtained.

  The olefin monomer which is one of the copolymerization raw materials of cyclic olefin type copolymer (m) is a monomer which addition-copolymerizes and gives frame | skeleton represented by said formula (I), and is the following general formula (Ia) It is an represented olefin.

In the above general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -Ethyl 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these, ethylene and propylene are preferable, and ethylene is particularly preferable, from the viewpoint of obtaining a crosslinked product (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 nonconjugated diene monomer which is one of the copolymerization raw materials of cyclic olefin type copolymer (m) is addition-copolymerized, and forms the structural unit represented by said Formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.

In the above general formula (IIIa), 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 as or different from each other, and 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, R 3 is a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and t is 0 to 10 R ⁷⁵ and R ⁷⁶ may be bonded together to form a monocyclic or polycyclic ring.

Although it does not specifically limit as a cyclic nonconjugated diene represented by said general formula (IIIa), For example, the cyclic nonconjugated diene represented by the following chemical formula can be mentioned. These Among 5-vinyl-2-norbornene, 8-vinyl-9-methyl-tetracyclo [4.4.0.1 ^{2, 5. 17,10} !-3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

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

N in 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, R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms It is.

  The cyclic olefin-based copolymer (m) of the present embodiment includes a structural unit derived from a cyclic non-conjugated diene represented by the general formula (III), so that it is other than the side chain portion, that is, the main chain of copolymerization. Is characterized by having a double bond in the moiety of

  The cyclic olefin monomer which is one of the copolymerization raw materials of cyclic olefin type copolymer (m) addition-copolymerizes, and forms the structural unit represented by the said 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 above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same as or different from each other, and 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, It is a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. .

As specific examples of the cyclic olefin represented by the above general formula (Va), the compounds described in WO 2006/118261 can be used.
Examples of cyclic olefins represented by the above general formula (Va) include bicyclo [2.2.1] -2-heptene (also called norbornene), tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene (also called 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, the modulus of elasticity of the copolymer and the crosslinked product can be easily maintained, and there is an advantage that the crosslinking can be easily controlled since they do not contain different double bond structures.

  Solubility of the cyclic olefin copolymer (m) in the solvent by using the olefin monomer represented by the above-mentioned general formula (Ia) or the cyclic olefin represented by the general formula (Va) as the copolymerization component The moldability is improved, and the yield of the product is improved.

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

In the general formula (VIa), x and d are 0 or an integer of 1 or more, preferably 0 to 2 integer, more preferably 0 or 1, y and z is 0, 1 or ^{2, R 81} -R ⁹⁹ may be the same as or different from each other, and a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, And a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or a carbon atom to which R ⁹¹ is bonded. And 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 aromatic It may form a ring.

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

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

  As specific examples of the cyclic olefins represented by the general formula (VIa) and the general formula (VIIa), the compounds described in paragraphs 0037 to 0063 of WO 2006/118261 can be used.

  Specific examples of the linear polyene represented by the general formula (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1. 2,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene and the like. In addition, cyclizable polyenes cyclized from polyenes such as 1,3-butadiene and 1,5-hexadiene may be used.

  A cyclic olefin-based copolymer (m) is a constituent unit derived from the linear polyene represented by the above general formula (VIIIa), or a cyclic non-conjugated diene represented by the general formula (III) and a compound represented by the general formula (V) When it contains a constitutional unit derived from a cyclic olefin other than the cyclic olefin represented (for example, general formula (VIa), general formula (VIIa)), the content of the structural unit is represented by the above general formula (I) Or a repeating unit derived from one or more kinds of olefins, a repeating unit derived from one or more cyclic non-conjugated dienes represented by the above general formula (III), one or more cyclics represented by the above general formula (V) It is usually 0.1 to 100 mol%, preferably 0.1 to 50 mol%, with respect to the total number of moles of the repeating unit derived from olefin.

  Use of the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa) and the linear polyene represented by the general formula (VIIIa) as the copolymerization component Thus, the effects according to the present embodiment can be obtained, and the solubility of the cyclic olefin copolymer in the solvent is further improved, so that the formability is improved and the yield of the product is improved. Among these, cyclic olefins represented by general formula (VIa) or (VIIa) are preferable. Since these cyclic olefins have a rigid ring structure, the modulus of elasticity of the copolymer and the crosslinked product can be easily maintained, and there is an advantage that the crosslinking can be easily controlled since they do not contain different double bond structures.

  The comonomer content and the glass transition point (Tg) of the cyclic olefin-based copolymer (m) can be controlled by the preparation ratio of the monomers depending on the intended application. The Tg of the cyclic olefin-based copolymer (m) is usually 300 ° C. or less, preferably 250 ° C. or less, more preferably 200 ° C. or less, still more preferably 170 ° C. or less, particularly preferably 150 ° C. or less. The melt moldability of cyclic olefin copolymer (m) and the solubility to the solvent at the time of varnishing improve that Tg is below the said upper limit.

The limiting viscosity [η] of the cyclic olefin copolymer (m) measured in decalin at 135 ° C. is preferably more than 0.01 dl / g, more preferably 0.02 dl / g or more, still more preferably 0. It is more than 05 dl / g. A crosslinked product obtained by crosslinking the cyclic olefin-based copolymer (m) or the cyclic olefin-based copolymer composition according to the present embodiment that the intrinsic viscosity [η] exceeds or exceeds the above lower limit (Q The heat resistance and mechanical properties of the above can be further improved.
Further, the limiting viscosity [η] of the cyclic olefin copolymer (m) measured in decalin at 135 ° C. is preferably less than 0.20 dl / g, more preferably 0.19 dl / g or less, still more preferably It is 0.18 dl / g or less. When the limiting viscosity [η] is less than or less than the above upper limit value, the cyclic olefin-based copolymer (m) or the fiber substrate of the cyclic olefin-based copolymer composition according to the present embodiment at the time of circuit board preparation The formability such as the impregnation property and the wiring embedding property can be further improved.
The intrinsic viscosity [η] of the cyclic olefin copolymer (m) can be controlled by polymerization conditions such as a polymerization catalyst, cocatalyst, H ₂ addition amount, polymerization temperature and the like.

[Method for producing cyclic olefin copolymer (m)]
The cyclic olefin-based copolymer (m) according to the present embodiment can be produced, for example, according to the method for producing a cyclic olefin-based copolymer described in paragraphs 0075 to 0219 of WO 2012/046443. Details are omitted here.

[Cyclic olefin copolymer composition]
Next, the cyclic olefin copolymer composition of the embodiment according to the present invention will be described.
The cyclic olefin-based copolymer composition according to the present embodiment contains the cyclic olefin-based copolymer (m) according to the present embodiment as an essential component. Moreover, it is preferable that the cyclic olefin type copolymer composition which concerns on this embodiment further contains cyclic olefin type polymer (n) different from cyclic olefin type copolymer (m).
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) contained in the cyclic olefin copolymer composition of the present embodiment is 100% by mass, the cyclic olefin copolymer is used. The content of the united body (m) is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, still more preferably 20% by mass to 80% by mass, particularly preferably 25% by mass or more The content of the cyclic olefin polymer (n) is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and still more preferably 20% by mass to 80% by mass. % By mass or less, particularly preferably 25% by mass or more and 75% by mass or less.
Each component will be specifically described below.

(Cyclic olefin polymer (n))
The cyclic olefin polymer (n) is a cyclic olefin copolymer different from the cyclic olefin copolymer (m). Specifically, the cyclic olefin polymer (n) contains at least one selected from ethylene or a copolymer of α-olefin and cyclic olefin (n1) and a ring-opened polymer of cyclic olefin (n2) Is preferred. The cyclic olefin copolymer composition according to the present embodiment further includes the dielectric properties of a crosslinked product obtained by crosslinking the cyclic olefin copolymer composition by including the cyclic olefin polymer (n). It can be good.
Here, the above-mentioned copolymer (n1) preferably does not contain a repeating unit derived from a cyclic non-conjugated diene represented by the above general formula (III). In the present embodiment, the copolymer (n1) does not contain a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III), the total of the repeating units in the copolymer (n1) When the number of moles is 100 mol%, it means that the content of the repeating unit derived from the cyclic non-conjugated diene represented by the above general formula (III) is 0.05 mol% or less.
The number average molecular weight Mn of the cyclic olefin polymer (n) is preferably 10,000 or more. The dielectric property of a crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer composition according to the present embodiment that the number average molecular weight Mn of the cyclic olefin polymer (n) is not less than the above lower limit value And heat resistance and mechanical properties can be further improved.
The number average molecular weight Mn of the cyclic olefin polymer (n) is preferably 60,000 or less, more preferably 57,000 or less, still more preferably 55,000 or less. If the number average molecular weight Mn of the cyclic olefin polymer (n) is less than or equal to the above upper limit value, the impregnating property to the fiber base material during wiring of the circuit substrate of the cyclic olefin copolymer composition according to this embodiment The formability such as the embeddability can be further improved.
The number average molecular weight Mn of the cyclic olefin polymer (n) can be controlled by polymerization conditions such as a polymerization catalyst, cocatalyst, H ₂ addition amount, polymerization temperature and the like.

  As the copolymer (n1) of ethylene or α-olefin and cyclic olefin, for example, the polymers described in paragraphs 0030 to 0123 of WO 2008/047468 can be used.

  For example, a polymer having an alicyclic structure in at least a part of the repeating structural unit (hereinafter, also simply referred to as “a polymer having an alicyclic structure”) is an alicyclic structure in at least a part of the repeating unit of the polymer As long as it has a group structure, specifically, it is preferable to include a polymer having one or more types of structures represented by the following general formula (3).

（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 the formula (3), x and y each represent a copolymerization ratio and is a real number satisfying 0/100 ≦ y / x ≦ 95/5. X and y are molar standards.
n represents the number of substitution 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 hydrogen atom or a monovalent group selected from the group consisting of 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 hydrogen atom or a monovalent group selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms).
Each of R ^a , R ^b , R ^c and Q may be of one type, and may have two or more types in any ratio. )

In the above general formula (3), R ^a is preferably one or more bivalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, and more preferably n = 0 In the 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 R ^a 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 comprises ethylene or 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), R ^a is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms.
Each of R ^a and R ^b may be one type, and may have two or more types in any ratio.
x and y indicate the copolymerization ratio, and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. Preferably, 50/50 ≦ y / x ≦ 95/5, 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 cyclic olefin is preferably a copolymer consisting of ethylene and cyclic olefin, and the cyclic olefin is bicyclo [2.2.1] -2-heptene, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene, cyclopentadiene - one or two selected from the group consisting of acenaphthylene adduct - benzyne adducts and cyclopentadiene The above are preferable, and bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 ^2,5 . It is more preferable that it is at least one selected from (1, ^{7, 10} ) -3-dodecene.
As the copolymer (n1) of ethylene or α-olefin and cyclic olefin, a polymer having one or more kinds of structures represented by the above general formula (3) or a polymer represented by the above general formula (4) The cyclic olefin copolymer to be produced may be a hydrogenated polymer.

Further, as the copolymer (n1) of ethylene or α-olefin and cyclic olefin, a copolymer of α-olefin having 4 to 12 carbon atoms and cyclic olefin is also preferable. Examples of the copolymer of a C 4-12 α-olefin and a cyclic olefin include:
The polymers described in paragraphs 0056 to 0070 of 015/178145 can be used.
As a cyclic olefin which comprises the copolymer of a C4-C12 alpha-olefin and cyclic olefin, norbornene and substituted norbornene are mentioned, for example, A 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 and 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個は、水素原子ではない。）

(Wherein, 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 and 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 may be R ^{5 to} R ⁸ may be the same or different in each repeating unit when n is 2 or more, provided that n is 2 or more, provided that n is 0, R is ^At least one of ^{1 to} R ⁴ and R ^{9 to} R ¹² is not a hydrogen atom.)

The substituted norbornene represented by formula (A) will be described. R ^{1 to} R ¹² in the general formula (A) may be the same or different, 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, hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; and alkyl groups having 1 to 20 carbon atoms, which may be different from each other. , May be partially different, or all may be identical.

Further, specific examples of R ^{9 to} R ¹² include, for example, hydrogen atom; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl group; phenyl group and tolyl And substituted or unsubstituted aromatic hydrocarbon groups such as ethylphenyl, isopropylphenyl, naphthyl and anthryl; benzyl, phenethyl and other aralkyl groups having an aryl substituted on the alkyl group. These may be different from one another, may be different from one another, or all may be identical.

Specific examples of R ⁹ and R ¹⁰ or R ¹¹ and R ¹² integrally forming a divalent hydrocarbon group include, for example, an alkylidene group such as ethylidene group, propylidene group, isopropylidene group, etc. It can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² mutually form a ring, the formed ring may be a single ring or a multiple ring, and may be a multiple ring having a bridge. Or a ring having a double bond, or a ring consisting of a combination of these rings. In addition, 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 and 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 [5] 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 ring 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]} undec-3,7-diene or tricyclo [4.4.0.1 ^{2, 5]} undec-3,8-diene or their partial hydrogenated product (or Adduct of cyclopentadiene and cyclohexene) tricyclo [4.4.0.1 ^2,5 ] undec-3-ene; 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 Tricyclic ring such as Olefin; tetracyclo [4.4.0.1 ^{2, 5. 17 10} ] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-vinyltetracyclo [4, 4. 0.1 ^{2, 5} . 17 ¹⁰ ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-cyclic olefin tetracyclic such ene; 8-cyclopentyl-- tetracyclo [4.4.0.1 ^{2, 5.} 17 ¹⁰ ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 17 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 referred to as 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 . 110, 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} . [ ^13,16 ] ^-14-eicosene ; and polycyclic cyclic olefins such as tetramer of cyclopentadiene.

  Among them, alkyl substituted norbornene (for example, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl group), alkylidene substituted norbornene (for example, bicyclo substituted with one or more alkylidene group) [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-olefins having 4 to 12 carbon atoms that constitute a copolymer of an α-olefin having 4 to 12 carbons and a cyclic olefin include, for example, α-olefins having 4 to 12 carbons and at least a halogen atom. The C4-12 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, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Among 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 the present embodiment has 4 to 12 carbon atoms, assuming that the total of repeating units contained in the copolymer is 100% by mole. The ratio of repeating units derived from α-olefin is preferably 10 to 90 mol%, more preferably 15 to 80 mol%, and still more preferably 20 to 70 mol%.
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 of the repeating units contained in the copolymer is 100 mol%. The proportion of the repeating unit is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 85 mol%, and still more preferably 30 mol% to 80 mol%.

  The conditions of the polymerization process 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 can be obtained, and known conditions can be used. The polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted.

Moreover, as a cyclic olefin polymer (n), the ring-opened polymer (n2) of cyclic olefin can be used.
Examples of ring-opening polymers (n2) of cyclic olefins include ring-opening polymers of norbornene monomers and ring-opening weights of norbornene monomers and other monomers capable of ring-opening copolymerization. And coalesced as well as their hydrides and the like.

Examples of norbornene-based monomers include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent in the ring), tricyclo [4.3.01, 6.12,5] Deca-3,7-diene (common name dicyclopentadiene) and its derivative, 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name) Methanotetrahydrofluorene: also known as 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 derivatives thereof, and the like.
Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, an alkylidene group and the like. 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 . 17 ¹⁰ ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodec-3-ene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.

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

  The hydride of the ring-opened polymer of a norbornene-based monomer, and the hydride of the ring-opened polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization are generally the above-mentioned ring-opened It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel and palladium to a polymerization solution of a polymer to hydrogenate a carbon-carbon unsaturated bond.

  In the present embodiment, one kind of cyclic olefin polymer (n) may be used alone, or two or more kinds thereof may be used in combination.

(Elastomer)
The cyclic olefin copolymer composition according to the present embodiment may further contain an elastomer from the viewpoint of improving the dielectric properties in a high frequency region while improving the mechanical properties of the obtained crosslinked product.
When the content of the elastomer is 100 parts by mass of the whole of the cyclic olefin copolymer composition, it is from the viewpoint of improving the dielectric characteristics in a high frequency region while improving the mechanical characteristics of the obtained crosslinked product. It is preferable that it is 1 to 50 parts by mass.
The elastomer preferably contains, for example, one or more selected from styrene-based elastomers, ethylene / propylene elastomers, and diene-based elastomers.

Styrene-based elastomers include, for example, styrene / conjugated diene block copolymer resin (butadiene, isoprene etc. as conjugated diene), hydrogenated product of styrene / conjugated diene block copolymer resin (butadiene, isoprene etc. as conjugated diene), styrene · Triblock copolymer resins of conjugated dienes and styrenes (conjugated dienes such as butadiene and isoprene), styrenes, hydrogenated products of triblock copolymer resins of conjugated dienes and styrenes (such as butadiene and isoprenes as conjugated dienes), etc. It can be mentioned.
Examples of the ethylene-propylene elastomer include ethylene-propylene rubber, ethylene-propylene-diene rubber and the like.
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 may be 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 the range that does not impair the object of the present invention.
As the above additives, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, One or more additives selected from the group consisting of a clouding agent, an antiblocking agent, an impact agent, a surface wettability improving agent, a filler, a hydrochloric acid absorbent and a metal deactivator are mentioned.

  Examples of the heat resistant stabilizer include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous Acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) pentaerythritol Phosphite type heat resistant stabilizers such as diphosphites; Lactone heat resistant stabilizers such as reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one with o-xylene; 3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(methylene-2,4,6-triyl) tri-p-cresol, 1,3,5 -Trimethyl- 2,4,6-Tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. These heat resistant stabilizers include sulfur based heat resistant stabilizers, amine based heat resistant stabilizers etc. These may be used singly or in combination of two or more. Stabilizers and hindered phenolic heat stabilizers are preferred.

  As the above-mentioned weathering stabilizer, it is possible to use one or more compounds selected from light stabilizers, antioxidants, ultraviolet light absorbers and the like.

Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6, 6 6-Tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyl oxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) Ronate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,6 3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,6, 6-Tetramethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6,3 6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6- Bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1 -(2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N ' -Bis ( 2,2,6,6-Tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensation product , 2,2,6,6-Tetramethyl-4-hydroxypiperidine-N-oxyl, bis (2,2,6,6-tetramethyl-N-oxylpiperidine) sebacate, tetrakis (2,2,6,6 6-Tetramethyl-N-oxypiperidyl) butane-1,2,3,4-tetracarboxylate, 3,9-bis (1,1-dimethyl-2- (tris (2,2,6,6-tetra) Methyl-N-oxyl piperidyl-4-oxycarbonyl) butylcarbonyloxy) ethyl) 2,4,6,10-tetraoxalo spiro [5.5] undecane, 1,6-bis ( 2,2,6,6-Tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4 -Dichloro-6-tert-octylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino -S-triazine polycondensates, condensates of 2,2,6,6-tetramethyl-4-piperidinol with tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6, A condensate of 6-tetramethyl-4-piperidinol and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, 1,2,3 A condensate with 3,4-butanetetracarboxylic acid, a condensate with 1,2,2,6,6-pentamethyl-4-piperidinol and 1,2,3,4-butanetetracarboxylic acid, 1- [2 -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy]- 2,2,6,6-Tetramethylpiperidine (e.g., Sanol LS-2626, manufactured by Sanko Corporation), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalon Acid-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) (eg, Tinuvin 144, manufactured by BASF), bis (2,2 ', 6,6'-tetramethyl-4-piperidyl) Sebacate (for example, T INUVIN 770 (manufactured by BASF AG), poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-) Examples include tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] (for example, CHIMASSORB 944, manufactured by BASF Corporation) and the like.

  As said antioxidant, a phenolic antioxidant, phosphorus type antioxidant, sulfur type antioxidant, thioether type antioxidant etc. are mentioned, for example.

  Examples of the above-mentioned phenolic antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-. Acrylates described in JP-A-63-179953 and JP-A-1-168643, such as amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like Phenolic compounds; 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (6-t-butyl-m-creso 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3- 3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3, -Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Benzene, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane [ie, pentaerythrymethyl-tetrakis (3- (3,5-di- t Alkyl substituted phenolic compounds such as butyl-4-hydroxyphenyl propionate)], triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), tocophenol etc .; 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; It 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 above-mentioned phosphorus antioxidant include triphenyl phosphite, diphenyl isodecyl 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-tert-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-t-butylphenyl-di-tridecylphos Phyto), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis (diphenyl monoalkyl (C12-C15) phosphite), 1 , 1,3-Tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene di- Phosphite, cyclic neopentanetetrayl bis (isodecyl phosphite), cyclic neopentane tetrayl bis (nonyl phenyl) Nyl phosphite), cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite), cyclic neopentane tetrayl bis (2,4-dimethylphenyl phosphite), cyclic neopentane tetrane And diphosphite compounds such as ylbis (2, 6-di-t-butylphenyl phosphite). Among these, monophosphite type 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 above-mentioned sulfur-based antioxidants 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 and the like Can be mentioned.

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

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

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

  Examples of the salicylic acid ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-. Di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like can be mentioned.

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

  As said acrylate type ultraviolet absorber, an ethyl 2- cyano-3, 3-diphenyl acrylate, 2'-ethylhexyl 2- cyano-3, 3-diphenyl acrylate etc. are mentioned, for example.

  A complex salt of nickel or cobalt is usually used as the metal complex salt type ultraviolet light absorber. Specifically, nickel [2,2'thiobis (4-t-octyl) phenolate] normal butyl amine, nickel dibutyl dithiocarbamate, nickel bis [o-ethyl-3,5- (di-t-butyl-4- 4 And hydroxybenzyl)] phosphate, cobalt dicyclohexyl dithiophosphate, [1-phenyl, 3-methyl, 4-decanonyl, pyrazolate (5) 2] nickel and the like.

  Examples of the radiation-resistant agent include rosin, rosin derivatives (eg, hydrogenated rosin, disproportionated rosin, modified rosin such as polymerized rosin, and modified rosin esters thereof), terpene resin, terpene phenol resin, aromatic modified Terpene resin, hydrogenated terpene resin, aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, alicyclic petroleum resin, hydrogenated petroleum resin, alkylphenol resin and the like can be mentioned.

  Examples of the plasticizer include tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethyl phenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, dicresyl monoxylenyl phosphate , Arylalkyl phosphates, diphenyl monoxylenyl phosphates, mol phosphates, trioctyl phosphates, phosphate triester plasticizers such as tris (isopropylphenyl) phosphate; dimethyl phthalate, diethyl phthalate, phthalic acid Phthalates such as dibutyl, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, octyldecyl phthalate, butyl benzyl phthalate and the like Stel plasticizers; fatty acid monobasic acid ester plasticizers such as butyl oleate and glycerin monooleate ester; dibutyl adipate, adipic acid di-n-fatty acid dibasic acid plasticizers; dihydric alcohol ester plasticizers Agents; oxy acid ester plasticizers and the like.

Examples of the lubricant include waxes, oils, caprins, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, higher acid such as arachidic acid and behenic acid, or metal salts thereof, ie, lithium salts, Calcium salts, sodium salts, magnesium salts, potassium salts, etc., fatty alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, etc., caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitin Examples thereof include aliphatic amides such as acid amide and stearic acid amide, esters of fatty acid and alcohol, fluoroalkylcarboxylic acids or metal salts thereof, and fluorine compounds such as fluoroalkylsulfonic acid metal salts.
Examples of the above-mentioned waxes include mineral wax such as montan wax, peat wax, ozokerite / cerecin wax and petroleum wax, polyolefin wax such as polyethylene wax and polypropylene wax, Fischer-Tropsch wax, chemically modified hydrocarbon wax, substituted amide Examples include synthetic waxes such as waxes, vegetable waxes, animal waxes and the like.
Examples of the oil include aromatic oils, naphthenic oils, mineral oils of paraffinic oils, natural and synthetic oils such as vegetable oils and silicone oils, and the like. The silicone oil can use dimethylpolysiloxane having a viscosity of 10 to 5000 cSt, preferably 500 cSt.

  As the releasing agent, for example, lower (C1 to 4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4 to 30) (such as hydrogenated castor oil), glycol esters of fatty acids, Liquid paraffin and the like can be mentioned.

  Examples of the nucleating agent include sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, [phosphoric acid-2,2′-methylenebis (4,6-di-t-butyl Phenyl)] dihydroxyaluminum, bis [phosphoric acid-2,2'-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphoric acid-2,2'-methylene bis (4,6 -Di-tert-butylphenyl)] aluminum, sodium-bis (4-tert-butylphenyl) phosphate, metal salts of benzoates such as sodium benzoate, aluminum p-tert-butylbenzoate, 1,3: 2,4 -Bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (O-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O-ethylbenzyl) Phenyl) sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidenesorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol, 1, 3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol, 1,3-O- 3,4-Dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,3: 2,4-bis (Op-chlorobenzylidene) sorbitol, mixtures thereof and the like can be mentioned.

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

As said flame retardant, a halogen type flame retardant, a phosphorus type flame retardant, a nitrogen-containing flame retardant, and an antimony type flame retardant can be used, for example.
As the halogen-based flame retardant, various chlorine- and bromine-based flame retardants can be used, but the flame-retardant effect, heat resistance at molding, dispersibility in resin, influence on physical properties of resin, etc. From the aspect, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide Decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [eg, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobi Phenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether), etc.], tetrabromobisphenol S, and derivatives thereof [eg, Tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc., tetrabromophthalic anhydride, and derivatives thereof [eg, tetrabromophthalimide, ethylene bistetrabromophthalimide Etc., ethylene bis (5,6-dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, a diester of hexachlorocyclopentadiene・ Alder reaction adducts, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bistribromophenyl ether, ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy Brominated flame retardants such as resins, brominated polycarbonates, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine, etc .; Chlorinated paraffins such as chlorinated paraffins It is preferred to use a flame retardant.

Examples of the phosphorus-based flame retardant include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate and tris (bromo) Halogenated phosphoric acid such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate and tris (tribromoneopentyl) phosphate Ester flame retardants; aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, etc .; triphenyl phosphate, cresyl di (Denyl phosphate, dicresyl phenyl phosphate, tricresyl fluorophosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tri (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenyl phenyl phosphate, tri (trimethylphenyl) phosphate, tri (trimethylphenyl phosphate) Non-halogenated phosphoric acid ester flame retardants such as aromatic phosphoric acid esters such as t-butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate and octyl diphenyl phosphate; Aluminum phosphinate flame retardants such as aluminum dimethylphosphinate and aluminum diethylphosphinate Can be 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, and 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, polyphosphate Examples thereof include acid melamine, melam, melem and melamine sulfate.
Examples of the antimony-based flame retardant include antimony oxide, antimony trioxide, antimony pentoxide, antimony tetraoxide, sodium antimonate and the like.

  As the above-mentioned foaming agent, a foaming agent generally used in foam molding of rubber can be widely used. Specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, etc. Inorganic foaming agents, nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexyl Azo compounds such as nitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), sulfonylsulfone such as diphenyl sulfone-3,3'-disulfonylhydrazide 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 cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants and the like.

  Examples of the cationic surfactant include tetraalkyl ammonium salts such as lauryl trimethyl ammonium chloride and stearyl trimethyl ammonium 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, sodium hexadecane sulfonate , Heptadencan sulfonate sodium, sodium octadecane sulfonate, sodium nonadecane sulfonate, sodium eiikosan sulfonate, potassium decane sulfonate, potassium undecane sulfonate, potassium dodecane sulfonate, potassium tridecane sulfonate, tetradecane sulfonate Potassium, potassium pentadecanesulfonate, potassium hexadecanesulfonate, potassium heptadecanesulfonate, octadecane sulfone Alkyl sulfonates such as potassium acid, potassium nonadecane sulfonate, potassium eeicosan deca sulfonate, sodium decylbenzene sulfonate, sodium undecylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, tetratetra Examples thereof include alkylbenzene sulfonates such as sodium decylbenzene sulfonate, sodium pentadecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, sodium heptadecyl benzene sulfonate, sodium octadecyl benzene sulfonate, alkyl phosphate and the like.

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

  Examples of the nonionic surfactants include monoglycerides of lauric acid, monoglycerides of palmitate, monoglycerides of stearic acid, monoglycerides of oleic acid, monoglycerides of behenic acid, monoglycerides of caprylic acid, monoglycerides of caprylic acid, diglycerides of lauric acid, diglycerides of palmitic acid and stearic acid diglyceride. , Oleic acid diglyceride, behenic acid diglyceride, caprylic acid diglyceride, coconut fatty acid diglyceride, triglyceride of lauric acid, triglyceride of palmitate, triglyceride of stearic acid, triglyceride of oleic acid, triglyceride of behenate, triglyceride of caprilic acid, triglyceride of caprylic acid, pentaerythritol monolaurate , Pe Fatty acid esters of pentaerythritol such as taerythritol monostearate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetralaurate, etc., 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 such as polyethylene glycol fatty acid esters, lauric acid diethanolamide, stearic acid diethanolamide De, coconut fatty acid diethanolamide etc Diethanol amides.

  As said coloring agent, natural type, synthetic type various dye, inorganic type, various organic type pigments can be used arbitrarily, for example.

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

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

  Examples of the surface wettability improver include silane coupling agents such as vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and the like. Be

An inorganic filler, an organic filler, etc. are mentioned as said filler.
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 And barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide and the like. These may be used singly or in combination of two or more.

  Examples of the organic filler include starch and its derivatives, cellulose and its derivatives, pulp and its derivatives, paper and its derivatives, flour, okara, bran, coconut husk, coffee grounds, protein, phthalic acid, fat Group polybasic acid type, glycerin type, citric acid type, glycol type, olefin type low molecular weight polymer, 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-hydroxystearate Magnesium, zinc 12-hydroxystearate and the like. Further, 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-salicital-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, and N, N′-bis (bis (salicyloyl) hydrazine). 3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bis Examples include phenyl hydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide and the like.

(Preparation method of cyclic olefin copolymer composition)
The method for preparing a cyclic olefin copolymer composition according to the present embodiment comprises a cyclic olefin copolymer (m), and if necessary, a cyclic olefin polymer (n), an elastomer, and various additives. Can be prepared by mixing As a mixing method, a method of melt blending with an extruder or the like, or a suitable solvent, for example, a saturated hydrocarbon such as heptane, hexane, decane or cyclohexane; dissolved in an aromatic hydrocarbon such as toluene, benzene or xylene, The solution blending method etc. which are made to disperse | distribute are employable.

[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 to the cyclic olefin copolymer (m) and the cyclic olefin polymer (n). Those preferably used as the solvent include, for example, saturated hydrocarbons such as heptane, hexane, octane and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene; and aromas such as toluene, benzene, xylene, mesitylene and pseudocumene Group hydrocarbons; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone and other ketone solvents; methyl Cellsolves such as cellsolve and ethyl cellsorb; 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 may be used alone or in combination of two or more in any proportion.

In the present embodiment, the method of producing the varnish may be carried out by any method, but usually includes a step of mixing the cyclic olefin copolymer composition and a solvent. About mixing of each component, there is no restriction | limiting in the order, It can implement by any system, such as batch or division. The apparatus for preparing the varnish is not limited and may be carried out by any apparatus of stirring, mixing, batch type or continuous type. The temperature at the time of preparing a varnish can be arbitrarily selected in the range from room temperature to the boiling point of a solvent.
The varnish may be prepared by using the reaction solution obtained when the cyclic olefin copolymer (m) is obtained as it is as a solvent, and dissolving the cyclic olefin polymer (n) therein. Alternatively, the varnish may be prepared by mixing a varnish of a cyclic olefin polymer (n) separately prepared with the reaction solution when the cyclic olefin copolymer (m) is obtained.

[Method for producing crosslinked product (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. Obtained by The crosslinking method of the cyclic olefin copolymer (m) is not particularly limited, while forming into an arbitrary form using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, electron beam or other radiation, Or the method of bridge | crosslinking after shaping | molding etc. are mentioned.

  The crosslinking method by a radical polymerization initiator can apply the crosslinking method by the normal radical polymerization initiator currently applied by polyolefin as it is. That is, a radical polymerization initiator such as dicumyl peroxide is added to the cyclic olefin copolymer composition, and heating and crosslinking are carried out. Although the blending ratio of the radical polymerization initiator is not particularly limited, it is usually 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, per 100 parts by mass of the cyclic olefin copolymer (m). Preferably, it is 0.5 to 10 parts by mass. The dielectric properties of the crosslinked product (Q) are improved when the blending ratio of the radical polymerization initiator is less than or equal to the above upper limit, and the heat resistance and mechanical properties of the crosslinked product (Q) are improved when it is greater than or equal to the above lower limit. It can be done.

  As the radical polymerization initiator, known thermal radical polymerization initiators, photo radical polymerization initiators, and these can be used in combination. Among these radical polymerization initiators, when a heat 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. As such an initiator, for example, dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis (t-butylperoxy) 2,5-dimethylhexane, 2,5-bis (t-butylperoxy) Dialkyl peroxides such as 2, 5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, bis (α-t-butylperoxyisopropyl) benzene, etc .; 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, Peroxyketals such as 6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; bis (t-butylperoxy) isophthalate, t-butylperoxybenzoate, t- Peroxy esters such as butyl peroxy acetate; 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- Trioxespan etc. are mentioned.

  Among the radical polymerization initiators, specifically, the photo radical polymerization initiator may, for example, be benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- And benzophenone, methyl benzoyl formate, isopropyl thioxanthone, and mixtures of two or more thereof. Further, sensitizers can be used together with these photo radical polymerization initiators. Examples of sensitizers 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 and the like Nitrogen compounds and the like can be mentioned.

In the case of crosslinking with sulfur or the like, the cyclic olefin-based copolymer composition is mixed with a sulfur-based compound and, if necessary, a vulcanization accelerator and a vulcanization acceleration auxiliary, and heated to carry out a crosslinking reaction. The compounding amount of the sulfur-based compound is not particularly limited, but from the aspect of promoting the crosslinking reaction efficiently, measuring the physical properties of the obtained crosslinked product, and economy, etc. 100 mass of cyclic olefin-based copolymer (m) It is used in a range of usually 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and in the case of using a vulcanization accelerator and a vulcanization acceleration auxiliary in combination, it is usually 0.1 to 20 It is used in parts by mass, preferably in the range of 0.2 to 10 parts by mass.
Various known sulfur compounds can be used to cause the crosslinking reaction, and examples thereof include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate Etc. Various vulcanization accelerators may also be used, such as N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N-diisopropyl-2-benzothiazole -Sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, thiazole system such as benzothiazyl-disulfide; A guanidine system such as diphenyl guanidine, triphenyl guanidine, di-ortho-tolyl guanidine, orsotholyl biguanide, diphenyl guanidine phthalate and the like; acetaldehyde-aniline reaction products; butyraldehyde-aniline condensates; hexamethylene tetrane , Aldehyde amines such as acetaldehyde ammonia, or aldehyde-ammonia type; imidazolines such as 2-mercapto imidazoline; thiocarbanilide, diethylthiourea dibutylthiourea, trimethylthiourea, thiourea series such as diorthotolylthiourea, etc .; tetramethyl thiuram Thiuram 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, Dime Le dithiocarbamate selenium, dithio acid salt-based tellurium diethyldithiocarbamate and the like; dibutyl xanthate acid zinc xanthate system; and the like. Vulcanization accelerating assistants include metal oxides such as zinc oxide, active zinc flower, zinc carbonate, complex zinc flower, magnesium oxide, magnesium oxide, lithium tin, basic lead carbonate, stearic acid, oleic acid, lauric acid, Examples thereof include fatty acid-based ones such as lead stearate and organic amine-glycol-based ones such as triethanolamine and diethylene glycol.

  The temperature at which the cyclic olefin copolymer composition is crosslinked at 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. The crosslinking may be carried out stepwise. Crosslinking can fully be advanced as it is more than the above-mentioned lower limit. Moreover, coloring of the crosslinked body obtained can be suppressed as it is below the said upper limit, or a process can be simplified. As a reference, polybutadiene, which is a typical double bond-containing polymer, can not generally be crosslinked under the conditions as described above, and requires crosslinking conditions at a high temperature such as 300 ° C.

  The cyclic olefin copolymer composition which concerns on this embodiment can also be bridge | crosslinked using the hydrosilyl group containing compound which has a hydrosilyl group at least 2 in 1 molecule. The crosslinking using the hydrosilyl group-containing compound can be performed, for example, according to the method described in JP-A-2015-193680. Details are omitted here.

  The method of crosslinking using an electron beam or other radiation has the advantage that there is no restriction on temperature during molding or flowability, and examples of radiation include γ rays and UV as well as 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 performed in combination with a crosslinking aid.

  The crosslinking aid is not particularly limited, but, for example, oximes such as p-quinonedioxime, 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, vinyl toluene, vinylpyridine; hexamethylenediallylnadiimide, 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 coagents may be used alone or in combination.

  The crosslinking reaction can also be carried out in the form of a mixture of a cyclic olefin copolymer composition and the above-mentioned radical polymerization initiator or a compound such as sulfur or a hydrosilyl group-containing compound, or the mixture is dissolved in a solvent The crosslinking reaction may be carried out in the form of a solution or in the form of a solution, or the solvent may be volatilized from the solution in a solvent to form a film, a coating or the like into any form, and then the crosslinking reaction may be further advanced.

  When the reaction is carried out in a molten state, the mixture of the 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. In addition, the crosslinking reaction can be further advanced after molding by any method.

  As a solvent used when performing reaction in a solution state, the solvent similar to the solvent used by the said solution blending method can be used.

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

[Film or sheet]
The crosslinked product of the cyclic olefin copolymer composition according to the present embodiment can be formed into a film or sheet and used for various applications. Various well-known methods are applicable as a method of forming a film or a sheet using the cyclic olefin type copolymer composition which concerns on this embodiment. For example, the method of forming by apply | coating the varnish mentioned above on support base materials, such as a thermoplastic resin film, drying, and heat-processing etc. and bridge | crosslinking a cyclic olefin type copolymer composition is mentioned. The method of applying the varnish to the support substrate is not particularly limited, and examples thereof include application using a spin coater, application using a spray coater, application using a bar coater, and the like.
Moreover, the method of melt-molding the cyclic olefin type copolymer composition which concerns on this embodiment, and obtaining a film or a sheet can also be mentioned.

[Laminate]
The said film or sheet which concerns on this embodiment can be used for various uses as a laminated body by laminating | stacking on a base material. Various well-known methods are applicable to the method of forming the laminated body which concerns on this embodiment.
For example, a laminate can be produced by laminating the film or sheet produced by the above-described method on a base material, and if necessary, heat curing with a press or the like.
In addition, a stacked body can also be manufactured by stacking an electrical insulating layer including the above-described cross-linked body on a conductor layer.

[Multilayer molded body or multilayer laminated film]
The cyclic olefin copolymer composition according to the present embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminated films. At this time, it is preferable that the resin layer formed of the cyclic olefin copolymer composition is 100 μm or less.
As various multilayer molded articles or multilayer laminated films, for example, multilayer molded articles for optical lenses in which the cyclic olefin copolymer composition of the present embodiment is formed on the surface of resin optical lenses, PET films, PE films, etc. The multilayer gas barrier film etc. in which the cyclic olefin type copolymer composition of this embodiment was formed in order to provide gas barrier property on the resin film surface are mentioned.

[Prepreg]
Further, the prepreg according to the present embodiment is formed by combining the cyclic olefin-based copolymer composition according to the present embodiment and a sheet-like fiber substrate.
It does not specifically limit as a manufacturing method of a prepreg, Various well-known methods are applicable. For example, the method includes a step of impregnating the sheet-like fiber substrate with the varnish described above to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the varnish.
The impregnation of the sheet-like fiber base material of the above-mentioned varnish, for example, a predetermined amount of varnish is a sheet by a known method such as spray coating method, dip coating method, roll coating method, curtain coating method, die coating method, slit coating method The protective film can be applied to the base fiber substrate, and if necessary, the protective film can be laminated thereon, and pressed from above with a roller or the like.
Further, the step of heating the above-mentioned impregnated body and drying the solvent contained in the above-mentioned varnish is not particularly limited, but for example, it is dried in air or nitrogen by a blower drier in batch mode or a heating furnace in a continuous step Methods such as drying by passing through and the like.
In the present embodiment, after impregnating the sheet-like fiber base material with the varnish, the solvent contained in the varnish is evaporated by heating the obtained impregnated body to a predetermined temperature, 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 there is no particular limitation. For example, PET (polyethylene terephthalate) fibers, aramid fibers, ultrahigh molecular weight polyethylene Organic fiber such as fiber, polyamide (nylon) fiber, liquid crystal polyester fiber, etc .; Inorganic fiber such as glass fiber, carbon fiber, alumina fiber, tungsten fiber, tungsten fiber, molybdenum fiber, titanium fiber, steel fiber, boron fiber, silicon carbide fiber, silica fiber And the like. Among these, organic fibers and glass fibers are preferable, and in particular, aramid fibers, liquid crystal polyester fibers, and glass fibers are preferable. As glass fiber, E glass, NE glass, S glass, D glass, H glass, T glass etc. can be mentioned.
Impregnation of the sheet-like fiber substrate with the varnish is carried out, for example, by immersion and application. The impregnation may be repeated several times as needed.
These sheet-like fiber substrates can be used singly or in combination of two or more, and the amount thereof 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.

  The thickness of the prepreg according to the present embodiment is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0. It is 5 mm. Within this range, the properties such as the formability at the time of lamination and the mechanical strength and toughness of the laminate obtained by curing are sufficiently exhibited, which is preferable.

[Circuit board]
As described above, the cyclic olefin-based copolymer composition according to the present embodiment can be suitably used for a circuit board because it is excellent in dielectric properties, heat resistance, mechanical properties and the like.
The circuit substrate can be produced by a generally known method and is not particularly limited. For example, the film, sheet or prepreg produced by the above method is heat-cured by a lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulation layer by a known method to prepare a laminate. Thereafter, the circuit board can be obtained by circuit processing or the like of the conductor layer in the laminate.

  As a metal used as a conductor layer, metals, such as copper, aluminum, nickel, gold, silver, stainless steel, can be used. As a method of forming the conductor layer, for example, a method of thermally fusing the metal to a foil or the like on an electrical insulating layer, a method of bonding the metal to a foil or the like using an adhesive agent Or the method of forming the conductor layer which consists of said metals on electric insulating layer by methods, such as sputtering, vapor deposition, plating, etc. are mentioned. As a mode of a circuit board, any of a single-sided board and a double-sided board may be sufficient.

Such a circuit board can be used as an electronic device, for example, by mounting an electronic component such as a semiconductor element. Electronic devices can be manufactured based on known information.
As such electronic devices, for example, ICT infrastructure devices such as servers, routers, super computers, mainframes, workstations, etc .; GPS antennas, antennas for wireless base stations, mm-wave antennas, antennas such as RFID antennas; mobile phones Communication devices such as smartphones, PHSs, PDAs, and tablet terminals; Personal computers, TVs, digital cameras, digital video cameras, POS terminals, wearable terminals, digital devices such as digital media players; Electronic control system devices, in-vehicle communication devices, cars Vehicle-mounted electronic devices such as navigation devices, millimeter wave radars, vehicle-mounted camera modules, etc .; semiconductor test devices, high frequency measuring devices, etc .;

[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 above-mentioned foaming agent may be added to the cyclic olefin copolymer composition.

[Use]
The cyclic olefin copolymer (m), 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, and thus the crosslinking For example, optical fiber, optical waveguide, optical disk base, optical filter, lens, optical adhesive, optical filter for PDP, coating material for organic EL, base film base of solar cell in aerospace field, solar Coating materials for batteries and thermal control systems, semiconductor elements, light emitting diodes, electronic elements such as various memories, hybrid ICs, MCMs, circuit boards, prepregs and laminates used to form insulating layers of circuit boards, display parts And other overcoat materials or interlayer insulation materials, substrates for liquid crystal displays and solar cells, medical instruments, automotive parts Mold release agent, resin modifier, transparent substrate for display, member for lithium ion battery, semiconductor process member, film capacitor, gas barrier coating material, wire coating material, member for automobile, member for aerospace, process material for semiconductor, wire Coating material, member for lithium ion battery, member for fuel cell, capacitor film, flexible display member, anchor coating material, transparent adhesive, modifier, cross-linking aid, medical container, medical catheter member, waterproof sealing material, It can be used in applications such as mold release materials, hard coat materials and foam modifiers.
In particular, since it is excellent in temporal stability of dielectric characteristics and excellent in solvent resistance, heat resistance, transparency, mechanical properties and the like, it can be suitably used for high frequency applications such as high frequency circuit boards. Furthermore, since it is excellent in gas barrier property, it can be used suitably as a substrate, film, or sheet of a liquid crystal display or a solar cell.

As mentioned above, although embodiment of this invention was described, these are the illustrations of this invention, and various structures other than the above can also be employ | adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

  Hereinafter, the present invention will be described in more detail by way of synthesis examples and examples, but the present invention is not limited thereby in any way.

  The composition and the limiting viscosity [η] of the cyclic olefin copolymer (m) used in the synthesis examples, examples and comparative examples were measured by the methods described below.

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 double bond carbon and the other peaks of hydrogen.

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

  The molded articles (films) obtained by the examples and comparative examples were evaluated by the methods described below.

  Evaluation of dielectric loss tangent: The dielectric loss tangent at 10 GHz was evaluated by the cylindrical cavity method for the films obtained by Examples and Comparative Examples. Here, when the dielectric loss tangent is 0.0045 or more, it was evaluated as NG.

  The following raw materials were used for the experiment.

Transition metal compound (1):
It synthesize | combined by the method of Unexamined-Japanese-Patent No. 2004-331965.

MMAO (made by Tosoh Finechem)
Toluene (Wako Pure Chemical Industries, Ltd .: Wako special grade)
Xylene (manufactured by Wako Pure Chemical Industries, Ltd .: Wako special grade)
5-vinyl-2-norbornene (made by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-Dodecene (made by Mitsui Chemicals, Inc.)
Acetone (manufactured by Wako Pure Chemical Industries, Ltd .: Wako special grade)
Methanol (manufactured by Wako Pure Chemical Industries, Ltd .: Wako special grade)

Cyclic olefin polymer (n):
Ethylene and tetracyclo [4.4.0.1 ^2,5 . Copolymer consisting of 1 ^{7, 10} ] -3-dodecene (Product name: APEL 6509 T, manufactured by Mitsui Chemicals, Inc., Mn = 44, 400)

Radical polymerization initiator:
Crosslinking agent 1: Percumil D (manufactured by NOF Corporation)

Cyclic olefin copolymer (m):
Synthesis Example 1 (Cyclic Olefin-Based Copolymer (m-1) (Mn = 37,000)))
1670 ml of xylene, 212 ml of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), tetracyclo [4.4.0.1 ^2,5 . 120 ml of 1 ^{7, 10} ] -3-dodecene (hereinafter also referred to as TD), 4 mmol of a toluene solution of MMAO (made by Tosoh Finechem) in terms of Al, and 1984 ml of hydrogen are inserted. It introduced until it became .6MPa. 0.04 mmol of transition metal compound (1) was dissolved in 10 ml of toluene and added to initiate polymerization. The pressure was maintained while continuously feeding ethylene gas, and polymerization was carried out at 25 ° C. for 60 minutes, and then 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 was added to precipitate all the polymer, and after stirring, it was filtered through a filter paper. This operation was repeated until the reaction product disappeared, and all the polymers obtained were dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / TD / VNB copolymer. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 25.7 mol%, the composition ratio of the TD-derived structure was 10.6 mol%, and the number average molecular weight (Mn) determined by GPC was 37,000. In addition, the intrinsic viscosity [η] was 0.43 dl / g.

Synthesis Example 2 (Cyclic Olefin-Based Copolymer (m-2) (Mn = 15, 500))!
Ethylene, 5-vinyl-2-norbornene (VNB), tetracyclo [4.4.0.1 ^2,5 . The copolymerization reaction with [ ^17,10 ] -3-dodecene (TD) was carried out continuously. Specifically, the amount of transition metal compound (1) relative to toluene in the polymerization vessel used as the transition metal compound (1) is 0.028 mmol / L, MMAO in hexane solution (Tosoh Fine Chem Made in a quantity such that Al / transition metal compound (1) = 300 (mol / mol). In addition, the amount of VNB / ethylene = 1.4 (mol / mol), TD / ethylene = 0.74 (mol / mol) and hydrogen / ethylene = 0.077 (mol / mol) in the polymerizer. Supplied. The copolymerization reaction was continuously performed at a polymerization temperature of 25 ° C. and a polymerization pressure of 3.6 MPaG.
The obtained polymer solution was introduced into an acetone / methanol (= 3/1) mixed solvent to which 0.1 vol% of concentrated hydrochloric acid was added to precipitate a polymer, and after stirring, it was filtered through a filter paper. The obtained solid was dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / TD / VNB copolymer. The compositional ratio of the VNB-derived structure in the polymer determined by NMR was 25.4 mol%, the composition ratio of the TD-derived structure was 12.4 mol%, and the number average molecular weight (Mn) determined by GPC was 15,500. In addition, the intrinsic viscosity [η] was 0.19 dl / g.

Synthesis Example 3 (Cyclic Olefin-Based Copolymer (m-3) (Mn = 11, 100)))
The concentration of the transition metal compound (1) is 0.031 mmol / L, VNB / ethylene = 1.1 (mol / mol), TD / ethylene = 0.57 (mol / mol), hydrogen / ethylene = 0.13 (mol) An ethylene / TD / VNB copolymer was obtained in the same manner as in Synthesis Example 2 except that it was changed to (mol / mol). The composition ratio of the VNB-derived structure in the polymer determined by NMR was 24.5 mol%, the composition ratio of the TD-derived structure was 10.8 mol%, and the number average molecular weight (Mn) determined by GPC was 11,100. In addition, the intrinsic viscosity [η] was 0.17 dl / g.

Synthesis Example 4 (Cyclic Olefin-Based Copolymer (m-4) (Mn = 6,070)))
The concentration of transition metal compound (1) is 0.027 mmol / L, VNB / ethylene = 1.1 (mol / mol), TD / ethylene = 0.57 (mol / mol), hydrogen / ethylene = 0.24 (mol) An ethylene / TD / VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that it was changed to (mol / mol). The composition ratio of the VNB-derived structure in the polymer determined by NMR was 25.3 mol%, the composition ratio of the TD-derived structure was 12.4 mol%, and the number average molecular weight (Mn) determined by GPC was 6,070. In addition, the intrinsic viscosity [η] was 0.11 dl / g.

Synthesis Example 5 (Cyclic Olefin-Based Copolymer (m-5) (Mn = 1, 200)))
The concentration of transition metal compound (1) is 0.027 mmol / L, VNB / ethylene = 1.1 (mol / mol), TD / ethylene = 0.57 (mol / mol), hydrogen / ethylene = 0.48 (mol) An ethylene / TD / VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that it was changed to (mol / mol). The composition ratio of the VNB-derived structure in the polymer determined by NMR was 24.7 mol%, the composition ratio of the TD-derived structure was 10.6 mol%, and the number average molecular weight (Mn) determined by GPC was 1,200. In addition, the intrinsic viscosity [η] was 0.01 dl / g.

<Number average molecular weight (Mn)>
The number average molecular weight (Mn) of the cyclic olefin copolymer (m) was measured by GPC measurement and determined as a standard polystyrene conversion value. GPC measurement was performed under the following conditions.
Device: GPC HLC-8321 (made by Tosoh Corporation)
Solvent: o-Dichlorobenzene Column: TSKgel GMH6-HT × 2, TSKgel GMH6-HTL × 2 (all are manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 1 mg / mL o-dichlorobenzene solution temperature: 140 ° C.

Example 1
(Preparation of varnish 1)
The cyclic olefin-based copolymer (m-1) obtained in Synthesis Example 1, Park Mill D manufactured by NOF Corporation as a radical polymerization (crosslinking) initiator, and xylene as a solvent were weighed according to the composition shown in Table 1. The weighed sample was placed in a 200 ml separable flask and stirred with a stirring blade at a rotational speed of 200 rpm for 4 hours until it was sufficiently dissolved, to obtain the desired varnish-like cyclic olefin copolymer composition . In addition, the unit of the compounding ratio of each raw material in Table 1 is a mass part.

(Film deposition)
The resulting varnish-like cyclic olefin copolymer composition is coated on a mold-released PET film at a speed of 10 mm / sec, and then dried at 150 ° C. for 4 minutes in a blower dryer under a nitrogen stream. did. Two obtained films were stacked, pressurized to 3.5 MPa with a vacuum press, heated from room temperature (25 ° C.) at a constant rate, and held at 180 ° C. for 120 minutes to obtain a laminated film. The dielectric loss tangent measurement was performed about the obtained laminated film. The obtained results are shown in Table 1.

(Formability evaluation)
A varnish obtained by the same method as the above varnish 1 except that a radical polymerization initiator was not added was coated on a release-treated PET film to obtain a cyclic olefin copolymer composition film. Ten sheets of the obtained film are stacked, and a viscoelasticity measuring apparatus MCR302 (manufactured by Anton Paar Co., Ltd.), using a parallel plate of 8 mmφ as a measuring jig, measuring frequency 1 Hz, heating rate 6 ° C./min, from room temperature to 200 ° C. The melt visco-elasticity measurement was performed to determine the melt viscosity (complex viscosity) [Pa · sec] at 180 ° C.
Here, when the melt viscosity at 180 ° C. is in the range of 50 Pa · sec or more and 1500 Pa · sec or less, the moldability is excellent because it is excellent in the formability such as the impregnating ability to the fiber substrate at the time of circuit board preparation The evaluation of was "○". When the melt viscosity at 180 ° C. is in the range of more than 1,500 Pa · sec, the formability is inferior, because the formability such as the impregnating ability to a fiber substrate and the wiring embedding property at the time of circuit board production is inferior.

[Examples 2 to 4 and Comparative Examples 1 to 3]
Except that the composition was changed to the composition shown in Table 1 (however, the varnish used for the evaluation of formability did not contain a radical polymerization initiator) produced a film in the same manner as in Example 1 and evaluated each Carried out. The obtained results are shown in Table 1. In Comparative Example 3, the formability was not evaluated because the dielectric loss tangent was evaluated as NG.

Claims (12)

(A) One or more olefin-derived repeating units represented by the following general formula (I):
(B) Repeating units derived from one or more cyclic non-conjugated dienes represented by the following general formula (III):
(C) A cyclic olefin-based copolymer (m) containing one or more cyclic olefin-derived repeating units represented by the following general formula (V),
When the total number of moles of repeating units in the cyclic olefin copolymer is 100 mol%,
The content of the repeating unit (B) derived from the cyclic non-conjugated diene is 19 mol% or more and 36 mol% or less,
The number average molecular weight Mn of the cyclic olefin copolymer is in the range of 3,000 to 16,000,
Cyclic olefin copolymer having a crosslinkable group.

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

[In the above general formula (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 identical to each other It may be different, and 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 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 It may form a single ring or multiple rings. ]

[In the above 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 identical to each other It may be different, and 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 And R ^{75 to} R ⁷⁸ may be bonded to each other to form a single ring or multiple rings. ] In the cyclic olefin copolymer according to claim 1,
When the total number of moles of repeating units in the cyclic olefin copolymer is 100 mol%, the content of the repeating unit (B) derived from the cyclic non-conjugated diene and the repeating unit (C) derived from the cyclic olefin Cyclic olefin-based copolymer whose total content is less than 40 mol%. In the cyclic olefin copolymer according to claim 2,
The cyclic nonconjugated diene constituting the repeating unit (B) derived from the cyclic nonconjugated diene contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the repeating unit (C) derived from the cyclic olefin is tetracyclo [4. 4.0.1 ^2,5 . The cyclic olefin type copolymer containing ^1,7,10 ] -3- dodecene.   A cyclic olefin-based copolymer composition comprising the cyclic olefin-based copolymer (m) according to any one of claims 1 to 3. In the cyclic olefin copolymer composition according to claim 4,
It further comprises a cyclic olefin-based polymer (n) different from the cyclic olefin-based copolymer (m),
The cyclic olefin polymer (n) is a copolymer of ethylene or an α-olefin and a cyclic olefin (n1) (wherein the copolymer (n1) is a cyclic non-cyclic polymer represented by the general formula (III)) Containing at least one selected from conjugated diene-based repeating units) and a ring-opened polymer of cyclic olefin (n2),
When the total amount of the cyclic olefin copolymer (m) and the cyclic olefin polymer (n) is 100 mass%,
The content of the cyclic olefin copolymer (m) is 5% by mass to 95% by mass, and the content of the cyclic olefin polymer (n) is 5% by mass to 95% by mass Copolymer composition.   A varnish comprising the cyclic olefin copolymer composition according to claim 4 or 5 and a solvent.   A crosslinked body obtained by crosslinking the cyclic olefin copolymer composition according to claim 4 or 5.   A film or sheet comprising the crosslinked body according to claim 7.   The laminated body which laminated | stacked the film or sheet | seat of Claim 8 on the base material.   A circuit board comprising: an electrical insulating layer containing the crosslinked body according to claim 7; and a conductor layer provided on the electrical insulating layer.   The electronic device provided with the circuit board of Claim 10.   A prepreg comprising the cyclic olefin copolymer composition according to claim 4 and a sheet-like fiber substrate.