JP2020105328A - Cyclic olefin-based copolymer, cyclic olefin-based copolymer composition, and cross-linked material - Google Patents

Abstract

To provide a cyclic olefin-based copolymer and a cyclic olefin-based copolymer composition, which can provide a cross-linked material having an excellent dielectric property in a high frequency region suitable for a circuit board and the like, and which has also excellent heat resistance.SOLUTION: Provided is a cyclic olefin-based copolymer (m), comprising: a repeating unit (A) derived from one or more olefins represented by general formula (I); a repeating unit (B) derived from one or more cyclic nonconjugated dienes represented by general formula (III); and a repeating unit (C) derived from one or more cyclic olefins represented by general formula (V). When the total number of moles of the repeating units in the cyclic olefin-based copolymer is set to 100 mol%, a total of the content of the repeating unit (B) derived from cyclic nonconjugated dienes and the content of the repeating unit (C) derived from cyclic olefins is in a range of 40.0 mol% to 50.0 mol%.SELECTED DRAWING: None

Description

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

In recent years, in addition to an increase in wireless communication devices and the like that use a high frequency band, a high frequency band is inevitably used due to an increase in communication speed. Accordingly, a circuit board having a small dielectric loss tangent is required to reduce transmission loss at high frequencies to the utmost.

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

Patent Documents 1 and 2 disclose that a sheet obtained by crosslinking a cyclic olefin 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 molding containing a crosslinkable cycloolefin polymer, which has excellent fluidity when heated.

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

According to the studies by the present inventors, the cyclic olefin-based copolymer having a crosslinkable group as described in Patent Document 1 or Patent Document 2 has a high glass transition temperature and a crosslinked product excellent in heat resistance is obtained. However, it became clear that the fluidity during heating tends to be poor. Therefore, the melt viscosity of the resin composition containing the cyclic olefin-based copolymer becomes high, sufficient fluidity cannot be obtained, and impregnation failure into the fiber base material or wiring embedding failure at the time of manufacturing the circuit board cannot be sufficiently suppressed. It became clear that there was a tendency.
In addition, it has been clarified that the crosslinkable resin molded article containing the crosslinkable cycloolefin polymer described in Patent Document 3 has good fluidity, but tends not to obtain sufficient heat resistance and mechanical strength. It was
From the above, there is room for improvement in the cyclic olefin-based copolymer having a crosslinkable group in that the heat resistance is improved while maintaining the excellent dielectric properties of the cyclic olefin-based copolymer.

The present invention has been made in view of the above circumstances, and it is possible to obtain a crosslinked body having excellent dielectric properties in a high frequency region suitable for a circuit board and the like, and a cyclic olefin-based copolymer having excellent heat resistance as well. The present invention provides a coalesced and cyclic olefin-based copolymer composition.

As a result of intensive investigations by the present inventors to solve the above problems, by specifying the composition of the repeating unit contained in the cyclic olefin-based copolymer, while satisfying the dielectric characteristics in the high frequency region required for the circuit board The inventors have found that a cyclic olefin-based copolymer having good heat resistance can be obtained, and completed the present invention.

That is, according to the present invention, the following cyclic olefin-based copolymer, cyclic olefin-based copolymer composition and cross-linked 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］
前記環状オレフィン由来の繰り返し単位（Ｃ）の含有量が１.０モル％以上１６.０モル％以下である［１］に記載の環状オレフィン系共重合体。
［３］
数平均分子量Ｍｎが３，０００以上３０，０００以下である［１］または［２］に記載の環状オレフィン系共重合体。
［４］
［１］乃至［３］のいずれか一項に記載の環状オレフィン系共重合体において、
前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、前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。
［５］
［１］乃至［４］のいずれか一項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。
［６］
［５］に記載の環状オレフィン系共重合体組成物と、溶媒と、を含有するワニス。
［７］
［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］
［７］に記載の架橋体を含むフィルムまたはシート。
［９］
［７］に記載の架橋体を含む積層体。
［１０］
［７］に記載の架橋体を含む電気絶縁層と、前記電気絶縁層上に設けられた導体層とを含む回路基板。
［１１］
［１０］に記載の回路基板を備えた電子機器。
［１２］
［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 repeating unit (A) derived from at least one olefin represented by the following general formula (I):
A repeating unit (B) derived from one or more cyclic non-conjugated dienes represented by the following general formula (III),
A cyclic olefin-based copolymer (m) comprising one or more cyclic olefin-derived repeating units (C) represented by the following general formula (V):
When the total number of moles of repeating units in the cyclic olefin-based copolymer is 100 mol %,
A cyclic olefin in which the total 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 in the range of 40.0 mol% or more and 50.0 mol% or less. Type copolymer.

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

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

[In the general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same as each other. They may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring. ]
[2]
The cyclic olefin-based copolymer according to [1], wherein the content of the repeating unit (C) derived from the cyclic olefin is 1.0 mol% or more and 16.0 mol% or less.
[3]
The cyclic olefin-based copolymer according to [1] or [2], which has a number average molecular weight Mn of 3,000 or more and 30,000 or less.
[4]
In the cyclic olefin-based copolymer according to any one of [1] to [3],
The cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the cyclic olefin-derived repeating unit (C) is tetracyclo[4. 4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene-containing cyclic olefin-based copolymer.
[5]
A cyclic olefin-based copolymer composition containing the cyclic olefin-based copolymer (m) according to any one of [1] to [4].
[6]
A varnish containing the cyclic olefin-based copolymer composition according to [5] and a solvent.
[7]
A crosslinked product obtained by crosslinking the cyclic olefin-based copolymer composition according to [5].
[8]
A film or sheet containing the crosslinked product according to [7].
[9]
A laminate comprising the crosslinked product according to [7].
[10]
A circuit board comprising an electric insulating layer containing the crosslinked product according to [7], and a conductor layer provided on the electric insulating layer.
[11]
An electronic device comprising the circuit board according to [10].
[12]
A prepreg containing the cyclic olefin-based copolymer composition according to [5] and a sheet-shaped fiber base material.

ADVANTAGE OF THE INVENTION According to this invention, it is possible to obtain the crosslinked body excellent in the dielectric property in a high frequency area suitable for a circuit board etc., and also the cyclic olefin type copolymer excellent in heat resistance, and a cyclic olefin type copolymer. 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 specified.

[Cyclic Olefin Copolymer (m)]
First, the cyclic olefin-based copolymer (m) of the embodiment according to the present invention will be described.
The cyclic olefin-based copolymer (m) according to the present embodiment is represented by one or more kinds of olefin-derived repeating units (A) represented by the following general formula (I) and the following general formula (III). A cyclic having a crosslinkable group containing one or more cyclic non-conjugated diene-derived repeating units (B) and one or more cyclic olefin-derived repeating units (C) represented by the following general formula (V): It is an olefin-based copolymer.

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

In the general formula (III), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or carbon. It 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 combine with each other to form a monocycle or polycycle.

In the general formula (V), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, 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 monocycle or polycycle.

Then, when the total number of moles of repeating units in the cyclic olefin-based 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 are The total content is 40.0 mol% or more and 50.0 mol% or less, preferably 40.5 mol% or more and 47.5 mol% or less, more preferably 41.0 mol% or more and 45.0 mol% or less. ..
When 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 within the above range, crosslinking obtained from the cyclic olefin-based copolymer (m) The body (Q) has excellent dielectric properties and heat resistance. Further, a crosslinked product (Q) having excellent mechanical properties, dielectric properties, transparency and gas barrier properties can be obtained. In other words, a crosslinked product having an excellent balance of these physical properties can be obtained.
When 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 at most the above upper limit, the moldability of the cyclic olefin-based copolymer (m) And the solubility are improved, and the stability over time of the dielectric properties of the crosslinked product (Q) is improved. When 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 at least the above lower limit value, the cyclic olefin-based copolymer (m) is crosslinked. The crosslinked product (Q) thus obtained has improved heat resistance and mechanical properties.

In the cyclic olefin-based copolymer (m) according to the present embodiment, when the total number of moles of the repeating units in the cyclic olefin-based copolymer (m) is 100 mol %, the cyclic olefin-derived repeating unit (C The content of) is preferably 1.0 mol% or more and 16.0 mol% or less, more preferably 2.0 mol% or more and 15.0 mol% or less, and further preferably 5.0 mol% or more and 14.0 mol%. % Or less.
When the content of the repeating unit (C) derived from a cyclic olefin is within the above range, the crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has excellent stability over time in dielectric properties and heat resistance. Also excellent in sex. Further, a crosslinked product (Q) having excellent mechanical properties, dielectric properties, transparency and gas barrier properties can be obtained. In other words, it is possible to obtain a crosslinked product (Q) having an excellent balance of these physical properties.

In the cyclic olefin-based copolymer (m), the content of the olefin-derived repeating unit (A) is preferable when the total number of moles of the repeating units in the cyclic olefin-based copolymer (m) is 100 mol %. Is 50.0 mol% or more and 60.0 mol% or less, more preferably 52.5 mol% or more and 59.5 mol% or less, and still more preferably 55.0 mol% or more and 59.0 mol% or less. Content of the repeating unit (B) derived from a conjugated diene is 24.0 mol% or more and 49.0 mol% or less, preferably 25.5 mol% or more and 45.5 mol% or less, more preferably 27.0 mol% or more. It is 40.0 mol% or less.
When the content of each repeating unit in the cyclic olefin-based copolymer (m) is within the above range, the crosslinked product (Q) obtained from the cyclic olefin-based copolymer (m) has stable dielectric properties with time. Excellent heat resistance. Further, a crosslinked product (Q) having excellent mechanical properties, dielectric properties, transparency and gas barrier properties can be obtained. In other words, it is possible to obtain a crosslinked product (Q) having an excellent balance of these physical properties.

The number-average molecular weight Mn of the cyclic olefin-based copolymer (m) is 3,000 or more, preferably 4,500 or more, more preferably 6,000 or more. When the number average molecular weight Mn of the cyclic olefin-based copolymer (m) is not less than the above lower limit, the cyclic olefin-based copolymer (m) or the cyclic olefin-based copolymer composition according to the present embodiment is cross-linked. It is possible to improve the dielectric properties, heat resistance, and mechanical properties of the crosslinked product (Q) obtained by.
The number average molecular weight Mn of the cyclic olefin-based copolymer (m) is 30,000 or less, preferably 25,000 or less, more preferably 20,000 or less. When the number average molecular weight Mn of the cyclic olefin-based copolymer (m) is not more than the above upper limit, the circuit board of the cyclic olefin-based copolymer (m) or the cyclic olefin-based copolymer composition according to the present embodiment is produced. At this time, it is possible to improve the moldability such as impregnation into the fiber base material and wiring embedding property.
The number average molecular weight Mn of the cyclic olefin copolymer (m) can be controlled by the polymerization conditions such as a polymerization catalyst, a cocatalyst, the amount of H ₂ added, and the polymerization temperature.

Here, when the number average molecular weight Mn of the cyclic olefin-based copolymer (m) is within the above range, the cyclic olefin-based copolymer (m) has excellent dielectric properties and fluidity and mechanical properties. In addition, it is possible to improve moldability such as impregnation into a fiber base material and wiring embedding at the time of manufacturing a circuit board.
Here, in the conventional cyclic olefin copolymer, when the number average molecular weight is within the above range, the molecular weight becomes relatively low, and thus the heat resistance of the obtained crosslinked product, dielectric properties, mechanical properties, etc. It tends to decrease. However, the cyclic olefin-based copolymer (m) according to the present embodiment has good impregnability into the fiber substrate 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, it is possible to suppress a decrease in mechanical strength.

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

In the general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 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 can be mentioned. 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 kinds of olefin monomers represented by the above formula (Ia) may be used.

The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials of the cyclic olefin-based copolymer (m), is addition-copolymerized to form the structural unit represented by the above 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 general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁶ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and t is 0 to 10 It is a positive integer and R ⁷⁵ and R ⁷⁶ may be bonded to each other to form a monocycle or polycycle.

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

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

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

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

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

In the general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, 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 monocycle or polycycle. ..

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 the cyclic olefin represented by the above general formula (Va) include bicyclo[2.2.1]-2-heptene (also referred to as norbornene), tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (also referred to as tetracyclododecene) is preferable, 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 elastic moduli of the copolymer and the crosslinked product are easily maintained, and since they do not contain a heterogeneous double bond structure, it is easy to control the crosslinking.

By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as the copolymerization component, the solubility of the cyclic olefin-based copolymer (m) in the solvent is improved. Is improved, the moldability is improved, and the product yield is improved.

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

In the general formula (VIa), x and d are 0 or an integer of 1 or more, preferably 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R ⁸¹ To R ^{99, which} may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group which is a cycloalkyl group having 3 to 15 carbon atoms, and the number of carbon atoms. A carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or a carbon atom to which R ⁹¹ is bonded, which is an aromatic hydrocarbon group or an alkoxy group of 6 to 20; May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other to form a monocyclic ring. Alternatively, it may form a polycyclic aromatic ring.

In 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, which} may be the same or different from each other, 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 is a branched hydrocarbon group, which may 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 chain 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. , 4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene and the like. Further, a cyclizable polyene obtained by cyclizing a polyene such as 1,3-butadiene or 1,5-hexadiene may be used.

The cyclic olefin-based copolymer (m) is a structural unit derived from the chain polyene represented by the general formula (VIIIa), or a cyclic non-conjugated diene represented by the general formula (III) and the general formula (V). When a structural unit derived from a cyclic olefin other than the represented cyclic olefin [eg, general formula (VIa), general formula (VIIa)] is contained, the content of the structural unit is represented by the general formula (I). One or more olefin-derived repeating units, one or more cyclic non-conjugated diene-derived repeating units represented by the general formula (III), and one or more cyclic units represented by the general formula (V) The amount is usually 0.1 to 100 mol %, preferably 0.1 to 50 mol% based on the total number of moles of repeating units 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 chain polyene represented by the general formula (VIIIa) as the copolymerization component. As a result, the effect according to the present embodiment is obtained, and the solubility of the cyclic olefin-based copolymer in the solvent is further improved, so that the moldability is improved and the product yield is improved. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferable. Since these cyclic olefins have a rigid ring structure, the elastic moduli of the copolymer and the crosslinked product are easily maintained, and since they do not contain a heterogeneous double bond structure, it is easy to control the crosslinking.

In the cyclic olefin-based copolymer (m), the comonomer content and the glass transition point (Tg) can be controlled by the charging ratio of the monomers depending on the intended use. The Tg of the cyclic olefin-based copolymer (m) is usually 300°C or lower, preferably 250°C or lower, more preferably 200°C or lower, still more preferably 170°C or lower, and particularly preferably 150°C or lower. When Tg is not more than the above upper limit, the melt moldability of the cyclic olefin-based copolymer (m) and the solubility in a solvent when forming a varnish are improved.

The intrinsic viscosity [η] of the cyclic olefin-based 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 at least 04 dl/g. When the intrinsic viscosity [η] exceeds or exceeds the above lower limit, a crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment. It is possible to further improve the heat resistance and mechanical properties of (1).
The intrinsic viscosity [η] of the cyclic olefin-based copolymer (m) measured in decalin at 135° C. is preferably less than 0.45 dl/g, more preferably 0.40 dl/g or less, and further preferably It is 0.35 dl/g or less. When the intrinsic viscosity [η] is less than or equal to the above upper limit value, the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment is applied to the fiber base material during the production of the circuit board. Moldability such as impregnation property and wiring embedding property can be further improved.
The intrinsic viscosity [η] of the cyclic olefin-based copolymer (m) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, hydrogenation amount and polymerization temperature.

[Production Method of 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-based copolymer composition according to the embodiment of 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, the cyclic olefin-based copolymer composition according to the present embodiment may further contain a cyclic olefin-based polymer (n) different from the cyclic olefin-based copolymer (m).
When the total amount of the cyclic olefin-based copolymer (m) and the cyclic olefin-based polymer (n) contained in the cyclic olefin-based copolymer composition of the present embodiment is 100% by mass, the cyclic olefin-based copolymer weight is The content of the coalescence (m) is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, further preferably 20% by mass or more and 80% by mass or less, particularly preferably 25% by mass or more. 75% by mass or less, and the content of the cyclic olefin polymer (n) is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, further preferably 20% by mass or more and 80% by mass or more. It is not more than 25% by mass, particularly preferably not less than 25% by mass and not more than 75% by mass.
Hereinafter, each component will be specifically described.

(Cyclic olefin polymer (n))
The cyclic olefin polymer (n) is a cyclic olefin polymer different from the cyclic olefin copolymer (m). Specifically, the cyclic olefin polymer (n) includes at least one selected from a copolymer (n1) of ethylene or α-olefin and a cyclic olefin and a ring-opening polymer (n2) of the cyclic olefin. It is preferable. The cyclic olefin-based copolymer composition according to the present embodiment further contains the cyclic olefin-based polymer (n) to further improve the dielectric properties of the crosslinked product obtained by crosslinking the cyclic olefin-based copolymer composition. It can be good.
Here, it is preferable that the copolymer (n1) does not contain a repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III). In the present embodiment, the fact that the copolymer (n1) does not contain the repeating unit derived from the cyclic non-conjugated diene represented by the general formula (III) means that the total number of 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. When the number average molecular weight Mn of the cyclic olefin polymer (n) is at least the above lower limit, the dielectric properties of the crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer composition according to the present embodiment. The 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, and further preferably 55,000 or less. When the number average molecular weight Mn of the cyclic olefin polymer (n) is not more than the above upper limit, the cyclic olefin copolymer composition according to the present embodiment can be impregnated into a fiber base material and wiring when the circuit board is manufactured. Moldability such as embedding property can be further improved.
The number average molecular weight Mn of the cyclic olefin polymer (n) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, H ₂ addition amount and polymerization temperature.

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

For example, a polymer having an alicyclic structure in at least a part of the repeating structural unit (hereinafter, also simply referred to as “polymer having an alicyclic structure”), in which at least a part of the repeating unit of the polymer is an alicyclic structure. Any polymer having a group structure may be used, and specifically, it is preferable to include a polymer having one or more 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 represent copolymerization ratios and are real numbers satisfying 0/100≦y/x≦95/5. x and y are on a molar basis.
n represents the number of substitutions of the substituent Q, and is a real number satisfying 0≦n≦2.
^Ra 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 hydrocarbon groups 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 hydrocarbon groups having 1 to 10 carbon atoms).
Each of R ^a , R ^b , R ^c and Q may be one type, or may be two or more types in any proportion. )

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

ここで、式（７）中、ｐは、０〜２の整数である。

Here, in the formula (7), p is an integer of 0 to 2.

Further, the copolymer (n1) of ethylene or α-olefin and a cyclic olefin is a cyclic olefin-based copolymer represented by the following general formula (4). For example, it comprises a structural unit (A) derived from ethylene or 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 the 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 hydrocarbon groups having 1 to 10 carbon atoms.
Each of R ^a and R ^b may be one type, or may be two or more types in any ratio.
x and y represent copolymerization ratios and are real numbers that satisfy 5/95≦y/x≦95/5. It is preferably 50/50≦y/x≦95/5, and more preferably 55/45≦y/x≦80/20. x and y are on a molar basis.

The copolymer (n1) of ethylene or α-olefin and cyclic olefin is preferably a copolymer 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, one or two kinds selected from the group consisting of cyclopentadiene-benzyne adduct and cyclopentadiene-acenaphthylene adduct The above are preferable, and bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ^2,5 . More preferably, it is at least one selected from 1 ^7,10 ]-3-dodecene.
The copolymer (n1) of ethylene or α-olefin and a cyclic olefin is a polymer having one or more structures represented by the general formula (3) or represented by the general formula (4). The cyclic olefin-based copolymer may be a hydrogenated polymer.

Further, as the copolymer (n1) of ethylene or α-olefin and the cyclic olefin, a copolymer of α-olefin having 4 to 12 carbon atoms and the cyclic olefin is also preferable. Examples of the copolymer of an α-olefin having 4 to 12 carbon atoms and a cyclic olefin include those disclosed in International Publication No. 2
The polymers described in paragraphs 0056 to 0070 of 015/178145 can be used.
Examples of the cyclic olefin forming the copolymer of the α-olefin having 4 to 12 carbon atoms and the cyclic olefin include norbornene and substituted norbornene, and norbornene is preferable. The said cyclic olefin can be used individually by 1 type or in combination of 2 or more types.

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

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

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

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

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

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

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the ring formed may be a monocycle or a polycycle, or may be a polycycle having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings. Further, 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]hepta-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[ 2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5- propenyl - bicyclo [2.2.1] cyclic olefins 2 ring such as hept-2-ene; tricyclo [4.3.0.1 ^{2, 5]} deca-3,7-diene (trivial name: dicyclopentadiene ), tricyclo[4.3.0.1 ^2,5 ]deca-3-ene; tricyclo[4.4.0.1 ^2,5 ]undeca-3,7-diene or tricyclo[4.4.0. 1 ^2,5 ]undeca-3,8-diene or a partial hydrogenation product thereof (or an 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]hepta- 3-ring cyclic olefins such as 2-ene and 5-phenyl-bicyclo[2.2.1]hept-2-ene; tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-methylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-vinyl-tetracyclo [4,4.0.1 ^2,5. 1 ^7,10 ]dodec-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 4-ring cyclic olefin such as 1 ^7,10 ]dodec-3-ene; 8-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene; tetracyclo ^{[7.4.1 3,6.} 0 ^1,9 . 0 ^2,7] tetradeca -4,9,11,13- tetraene (1,4-methano -1,4,4a, also referred 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 . 1 ^10,13] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^{12, 16]} -5-eicosene, heptacyclo [8.7.0.1 ^2,9. 0 ^3,8 . 1 ^4,7 . 0 ^12,17 . 1 ^13,16 ] ^-14-eicosene ; polycyclic cyclic olefins such as a tetramer of cyclopentadiene.

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

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

The α-olefin having 4 to 12 carbon atoms is not particularly limited, but 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 them, 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 when the total of repeating units contained in the copolymer is 100 mol %. The proportion of repeating units derived from α-olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 80 mol% or less, and further preferably 20 mol% or more and 70 mol% or less.
Further, 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 repeating units contained in the copolymer is 100 mol %. The proportion of repeating units is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and further preferably 30 mol% or more and 80 mol% or less.

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

As the cyclic olefin polymer (n), a ring-opening polymer (n2) of cyclic olefin can be used.
Examples of the ring-opening polymer (n2) of a cyclic olefin include a ring-opening polymer of a norbornene-based monomer and a ring-opening weight of a norbornene-based monomer and another monomer capable of ring-opening copolymerization. Examples include coalesced products and hydrides thereof.

Examples of the norbornene-based monomer include bicyclo[2.2.1]hept-2-ene (conventional name: norbornene) and its derivatives (having a substituent on the ring), tricyclo[4.3.01]. 6.12,5]deca-3,7-diene (conventional name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.12,5]deca-3-ene (conventional name) Methanotetrahydrofluorene: 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (conventional 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 and an alkylidene group. In addition, the substituent may have one or two or more. Examples of the derivative having a substituent on such a ring include 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.

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

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

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

(Elastomer)
The cyclic olefin-based copolymer composition according to the present embodiment may further include an elastomer from the viewpoint of improving the mechanical properties of the resulting crosslinked product and improving the dielectric properties in the high frequency region.
The content of the elastomer is such that, when the total amount of the cyclic olefin-based copolymer composition is 100 parts by mass, the mechanical properties of the resulting crosslinked product are improved and the dielectric properties in the high frequency region are improved. It is preferably 1 part by mass or more and 50 parts by mass or less.
The elastomer preferably contains, for example, one or more selected from styrene elastomers, ethylene/propylene elastomers, and diene elastomers.

Examples of the styrene-based elastomer include styrene/conjugated diene block copolymer resin (such as butadiene and isoprene as the conjugated diene). Further, it can be used as a styrene elastomer exemplified in paragraphs [0082] and [0083] of International Publication No. 2017/150218.

(Additive)
Various additives may be added to the cyclic olefin-based copolymer composition according to the present embodiment depending on the purpose. The amount of the additive added is appropriately selected according to the application within the range that does not impair the object of the present invention.
Examples of the additives include heat stabilizers, weathering stabilizers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction/wear improvers, flame retardants, foaming agents, antistatic agents, colorants, and anti-static agents. One or more additives selected from the group consisting of a clouding agent, an antiblocking agent, an impact resistance agent, a surface wetting improver, a filler, a hydrochloric acid absorbent and a metal deactivator can be mentioned.

Examples of the heat resistance stabilizer include tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphite. Acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4′-diylbisphosphonite, and bis(2,4-di-tert-butylphenyl)pentaerythritol Phosphite heat-resistant stabilizers such as diphosphite; Lactone heat-resistant stabilizers such as reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and 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, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Examples thereof include hindered phenol heat resistance stabilizers, sulfur heat resistance stabilizers, amine heat resistance stabilizers, etc. These may be used alone or in combination of two or more. A phyto-type heat-resistant stabilizer and a hindered phenol-type heat-resistant stabilizer are preferred.

As the weather resistance stabilizer, one kind or two or more kinds of compounds selected from a light stabilizer, an antioxidant, an ultraviolet absorber and the like can be used.

Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. 6-tetramethyl-4-piperidyl benzoate, N-(2,2,6,6-tetramethyl-4-piperidyl)dodecyl succinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxyethyl]-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)malonate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,3 4-butanetetracarboxylate, tetrakis(1,2,2,6,6,-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6- Tetramethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)- 1,2,3,4-butanetetracarboxylate, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyl Oxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6- Pentamethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,5,8,12-tetrakis[4,6-bis{ N-(2,2,6,6-tetramethyl-4-piperidyl)butylamino}-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, 1-( 2-Hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro-s-triazine/N,N′-bi Sus(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine condensate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine/dibromo Ethane condensate, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxyl, bis(2,2,6,6-tetramethyl-N-oxylpiperidine) sebacate, tetrakis(2,2,2 6,6-Tetramethyl-N-oxypiperidyl)butane-1,2,3,4-tetracarboxylate, 3,9-bis(1,1-dimethyl-2-(tris(2,2,6,6 -Tetramethyl-N-oxylpiperidyl-4-oxycarbonyl)butylcarbonyloxy)ethyl) 2,4,6,10-tetraoxarospyro[5.5]undecane, 1,6-bis(2,2,6) 6-Tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6- Tertiary octylamino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate Condensate, 2,2,6,6-tetramethyl-4-piperidinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl- Condensation product of 4-piperidinol and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, tridecyl alcohol and 1,2,3,4-butane Condensate of tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 1,2,3,4-butanetetracarboxylic acid, 1-[2-[3-( 3,5-Di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-3,5-di-t-butyl-4-hydroxyphenyl]propionyloxy]-2,2,6 , 6-Tetramethylpiperidine (for example, Sanol LS-2626, Sankyo Co., Ltd.), 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid-bis-( 1,2,2,6,6-pentamethyl-4-piperidyl) (for example, Tinuvin 144, manufactured by BASF), bis(2,2′,6,6′-tetramethyl-4-piperidyl) sebacate (For example, TINUVIN770, manufactured by BASF), poly[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6 , 6-Tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino] (for example, CHIMASSORB944, manufactured by BASF).

Examples of the above-mentioned antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and thioether-based antioxidants.

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

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

Examples of the sulfur-based antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thio. Dipropionate, pentaerythritol-tetrakis-(β-lauryl-thio-propionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, etc. Are listed.

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

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

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-dodecaroxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxy benzophenone etc. are mentioned.

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

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

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

As the metal complex salt type ultraviolet absorber, a complex salt of nickel or cobalt is usually used. Specifically, nickel [2,2′ thiobis(4-t-octyl)phenolate] normal butylamine, nickel dibutyldithiocarbamate, nickel bis[o-ethyl-3,5-(di-t-butyl-4-). Hydroxybenzyl)] phosphate, cobalt dicyclohexyldithiophosphate, [1-phenyl, 3-methyl, 4-decanonyl, pyrazolate(5)2] nickel and the like.

Examples of the radiation resistant agent include rosin. Further, the radiation resistant agent exemplified in paragraph [0099] of International Publication No. 2017/150218 can be used.

Examples of the plasticizer include tricresyl phosphate and the like. Further, the plasticizers exemplified in paragraph [0100] of International Publication No. 2017/150218 can be used.

Examples of the lubricant include waxes. Further, the lubricants exemplified in paragraph [0101] of International Publication No. 2017/150218 can be used.

Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened castor oil, etc.), 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. Further, the nucleating agent exemplified in paragraph [0103] of International Publication No. 2017/150218 can be used.

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

As the flame retardant, for example, a halogen flame retardant, a phosphorus flame retardant, a nitrogen-containing flame retardant, or an antimony flame retardant can be used.
As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but flame retardant effect, heat resistance during molding, dispersibility in resin, influence on physical properties of resin, etc. From the aspect, pentabromodiphenyl ether and the like can be mentioned. Further, the flame retardant exemplified in paragraph [0105] of International Publication No. 2017/150218 can be used.

Examples of the phosphorus-based flame retardant include tris(chloroethyl)phosphate. Further, the phosphorus-based flame retardants exemplified in paragraph [0106] of International Publication No. 2017/150218 can be used.

As the foaming agent, a foaming agent generally used when foam-molding rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, etc. Inorganic foaming agent, N,N′-dimethyl-N,N′-dinitrosoterephthalamide, and the like. Further, the foaming agent exemplified in paragraph [0107] of International Publication No. 2017/150218 can be used.

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

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

Examples of the anionic surfactant include sodium decane sulfonate and the like. Further, the anionic surfactants exemplified in paragraph [0110] of International Publication No. 2017/150218 can be used.

Examples of the amphoteric surfactant include lauryl betaine. Furthermore, the amphoteric surfactants exemplified in paragraph [0111] of International Publication No. 2017/150218 can be used.

Examples of the nonionic surfactant include lauric acid monoglyceride. Further, the nonionic surfactants exemplified in paragraph [0112] of WO 2017/150218 can be used.

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

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

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

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

Examples of the filler include inorganic fillers and organic fillers.
Examples of the inorganic filler include silica. Further, the filler exemplified in paragraph [0117] of International Publication No. 2017/150218 can be used.

Examples of the organic filler include starch and its derivatives. Further, the filler exemplified in paragraph [0118] of International Publication No. 2017/150218 can be used.

Examples of the hydrochloric acid absorbent include higher fatty acid metal salts. Specific examples include sodium stearate and the like. Further, the hydrochloric acid absorbents exemplified in paragraph [0119] of International Publication No. 2017/150218 can be used.

Examples of the metal deactivator include N,N′-diphenyloxamide. Further, the metal deactivator exemplified in paragraph [0120] of International Publication No. 2017/150218 can be used.

(Method for preparing cyclic olefin-based copolymer composition)
The method for preparing a cyclic olefin copolymer composition according to the present embodiment includes a cyclic olefin copolymer (m), if necessary, a cyclic olefin polymer (n), an elastomer, and various additives. It can be prepared by mixing and. As a mixing method, a method of melt blending with an extruder or the like, or a suitable solvent, for example, saturated hydrocarbon such as heptane, hexane, decane, and cyclohexane; dissolved in aromatic hydrocarbon such as toluene, benzene, and xylene, It is possible to employ a solution blending method or the like which is performed by dispersing.

[varnish]
The cyclic olefin-based copolymer composition according to this embodiment can be made into a varnish by mixing with a solvent.
The solvent for preparing the varnish is not particularly limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (m). Preferred examples of the solvent include saturated hydrocarbons such as heptane, hexane, octane and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene; aromatics such as toluene, benzene, xylene, mesitylene and pseudocumene. Group hydrocarbons; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone-based solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone; methyl Cellosolves such as cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate; halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene are used. .. Heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene and pseudocumene are preferably used. These solvents can be used alone or in combination of two or more kinds at any ratio.

In the present embodiment, the method for producing the varnish may be any method, but usually includes a step of mixing the cyclic olefin-based copolymer composition and a solvent. Regarding the mixing of the components, there is no limitation on the order, and they can be carried out by any method such as batch or division. The apparatus for preparing the varnish is not limited, and may be any apparatus capable of stirring and mixing, such as batch type or continuous type. The temperature for preparing the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.

[Method for producing crosslinked product (Q)]
The crosslinked product (Q) is a crosslinked product of the cyclic olefin-based copolymer composition according to the present embodiment, and crosslinks the cyclic olefin-based copolymer (m) in the above-mentioned cyclic olefin-based copolymer composition. It is obtained by The method for crosslinking the cyclic olefin-based copolymer (m) is not particularly limited, but using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, an electron beam or other radiation, while molding into an arbitrary shape, Alternatively, a method of crosslinking after molding may be used.

For the crosslinking with the radical polymerization initiator, the usual crosslinking method with the radical polymerization initiator applied to polyolefin can be applied as it is. That is, a radical polymerization initiator such as dicumyl peroxide is added to the cyclic olefin copolymer composition, and the mixture is heated and crosslinked. The mixing ratio of the radical polymerization initiator is not particularly limited, but is usually 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the cyclic olefin copolymer (m), and It is preferably 0.5 to 10 parts by mass. When the mixing ratio of the radical polymerization initiator is at most the above upper limit, the dielectric properties of the crosslinked product (Q) will be improved, and when it is at least the above lower limit, the heat resistance and mechanical properties of the crosslinked product (Q) will be improved. Can be made.

As the radical polymerization initiator, known thermal radical polymerization initiators, photoradical polymerization initiators and these can be used in combination. When a thermal radical polymerization initiator is used among these radical polymerization initiators, the 10-hour half-life temperature is usually 80° C. or higher, preferably 120° C. or higher from the viewpoint of storage stability. Examples of such an initiator include dicumyl peroxide, t-butyl cumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane and 2,5-bis(t-butylperoxide). (Oxy) 2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, bis(α-t-butylperoxyisopropyl)benzene, and other dialkyl peroxides; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-Butyl-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-bis(t-butylperoxy)butyrate, 3,3,6,6,9,9-hexamethyl-1, Peroxyketals such as 2,4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate; t- Hydroperoxides such as butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide and p-menthane hydroperoxide Bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane and the like.

Among the radical polymerization initiators, the photo radical polymerization initiators are specifically, for example, benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-. On, benzophenone, methyl benzoyl formate, isopropyl thioxanthone, and a mixture of two or more thereof. Further, a sensitizer can be used together with these photo radical polymerization initiators. Examples of the sensitizer include anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, carbonyl compounds such as p,p'-tetramethyldiaminobenzophenone and chloranil, nitrobenzene, p-dinitrobenzene, 2- Nitro compounds such as nitrofluorene, aromatic hydrocarbons such as anthracene and chrysene, sulfur compounds such as diphenyl disulfide, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene, etc. A nitrogen compound etc. can be mentioned.

In the case of crosslinking with sulfur or the like, a sulfur-based compound, optionally a vulcanization accelerator, and a vulcanization acceleration aid are added to the cyclic olefin-based copolymer composition and heated to carry out a crosslinking reaction. The amount of the sulfur-based compound to be added is not particularly limited, but 100% by mass of the cyclic olefin-based copolymer (m) is used from the viewpoint of efficiently promoting the crosslinking reaction, improving the physical properties of the resulting crosslinked product, and economical efficiency. It is usually used in the range of 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and usually 0.1 to 20 parts by mass when a vulcanization accelerator or a vulcanization acceleration aid is used in combination. It is used in the range of parts by mass, preferably 0.2 to 10 parts by mass.
Various known sulfur compounds can be used for causing the crosslinking reaction, and examples thereof include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Etc. Various vulcanization accelerators can be used, and N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole. -Thiazoles such as sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole and benzothiazyl-disulfide; Guanidine compounds such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, orthosultryl biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reaction products; butyraldehyde-aniline condensates; aldehydes such as hexamethylenetetramine and acetaldehyde ammonia. Amine or aldehyde-ammonia system; imidazoline system such as 2-mercaptoimidazoline; thiourea system such as thiocarbanilide, diethyl thiourea dibutyl thiourea, trimethyl thiourea, diorthoritolyl thiourea; tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide , A thiuram system such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, butylphenyldithiocarbamine. Examples thereof include zinc acid salts, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; dithioate salts; zanthate such as zinc dibutylxanthate; and the like. As the vulcanization accelerating aid, zinc oxide, active zinc white, zinc carbonate, complex zinc white, magnesium oxide, litharge, red lead, metal oxides such as basic lead carbonate, stearic acid, oleic acid, lauric acid, Examples thereof include fatty acid type such as lead stearate and organic amine/glycol type such as triethanolamine and diethylene glycol.

Crosslinking temperature of the cyclic olefin-based copolymer composition for both radical polymerization initiator cross-linking and sulfur cross-linking is usually 100 to 300°C, preferably 120 to 250°C, and more preferably 120 to 220°C. Cross-linking may be performed by changing it stepwise. When it is at least the above lower limit, crosslinking can be sufficiently advanced. Moreover, when it is at most the above upper limit, coloring of the obtained crosslinked product can be suppressed, or the process can be simplified. As a reference, polybutadiene, which is a typical double bond-containing polymer, cannot be generally crosslinked under the above conditions, and requires crosslinking conditions at a high temperature such as 300°C.

The cyclic olefin-based copolymer composition according to the present embodiment can also be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule. Crosslinking using a hydrosilyl group-containing compound can be carried out, for example, according to the method described in JP-A-2015-193680. Details are omitted here.

The method of cross-linking using an electron beam or other radiation has an advantage that the temperature and fluidity at the time of molding are not limited, and examples of radiation include electron rays, γ rays and UV. ..

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

The crosslinking aid is not particularly limited, but examples thereof include oximes such as p-quinonedioxime and p,p′-dibenzoylquinonedioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl. Methacrylate, acrylic acid/zinc oxide mixture, acrylates or methacrylates such as allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; hexamethylene diallyl nadimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl Allyl compounds such as monoglycidyl isocyanurate, triallyl cyanurate and triallyl isocyanurate; maleimides such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylenediphenylene)dimaleimide Examples of the compound include cyclic non-conjugated dienes such as vinyl norbornene, ethylidene norbornene and dicyclopentadiene. These crosslinking aids may be used alone or in combination.

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

When the reaction is carried out in a molten state, the raw material mixture is melted and kneaded using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader or a continuous mixer. Further, the crosslinking reaction can be further advanced after molding by any method.

As the solvent used when carrying out the reaction in a solution state, the same solvent as that used in the above 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.

[Crosslinked]
The crosslinked product (Q) according to the present embodiment has excellent dielectric properties and heat resistance.
The Tg of the crosslinked product (Q) according to this embodiment is preferably 140°C or higher, more preferably 150°C or higher, and further preferably 170°C or higher. The upper limit is not particularly limited, but may be, for example, 300° C. or lower.
The dielectric loss tangent at 10 GHz of the crosslinked product (Q) according to the present embodiment can be set to, for example, 0.0001 or more and 0.0050 or less.

[Film or sheet]
The crosslinked product of the cyclic olefin copolymer composition according to the present embodiment can be molded into a film or sheet and used for various purposes. Various known methods can be applied as a method for forming a film or sheet using the cyclic olefin-based copolymer composition according to the present embodiment. For example, a method may be mentioned in which the above-mentioned varnish is applied on a supporting substrate such as a thermoplastic resin film, dried, and then heat-treated to crosslink the cyclic olefin-based copolymer composition. The method of applying the varnish to the supporting substrate is not particularly limited, and examples thereof include coating using a spin coater, coating using a spray coater, and coating using a bar coater.
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 film or sheet according to the present embodiment can be used as a laminate for various purposes by laminating it on a substrate. Various known methods can be applied to the method for forming the laminate according to the present embodiment.
For example, a laminate can be prepared by laminating a film or sheet produced by the above-mentioned method on a base material and heat-curing it with a press or the like if necessary.
In addition, a laminated body can be produced by laminating the above-mentioned electrically insulating layer containing the crosslinked body on the conductor layer.

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

[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-shaped fiber base material.
The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, a method including a step of impregnating the sheet-shaped fiber base material with the above-mentioned varnish to obtain an impregnated body and a step of heating the obtained impregnated body and drying the solvent contained in the above-mentioned varnish.
The sheet-shaped fiber base material is impregnated with the varnish by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating with a predetermined amount of varnish. It can be carried out by applying it to a filamentous fiber substrate, stacking a protective film on it if necessary, and pressing it with a roller or the like from the upper side.
Further, the step of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited. For example, the impregnated body is dried in air or nitrogen by a blast dryer in a batch system, or in a continuous heating furnace. Examples of the method include drying by passing through.
In this embodiment, after the sheet-shaped fiber base material is impregnated with the varnish, the impregnated body thus obtained is heated to a predetermined temperature to evaporate the solvent contained in the varnish and obtain a prepreg.

Inorganic and/or organic fibers can be used as the fibers constituting the sheet-shaped fiber base material according to the present embodiment, and are not particularly limited, and examples thereof include PET (polyethylene terephthalate) fibers, aramid fibers, and ultra-high molecular polyethylene. Fibers, organic fibers such as polyamide (nylon) fibers and liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers and silica fibers , Etc. can be mentioned. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. Examples of the glass fiber include E glass, NE glass, S glass, D glass, H glass, T glass and the like.
Impregnation of the sheet-shaped fiber base material with the varnish is carried out, for example, by dipping and coating. The impregnation may be repeated multiple times if necessary.
These sheet-like fibrous base materials may be used alone or in combination of two or more kinds, and the use amount thereof is appropriately selected as desired, but is usually 10 to 90 mass in the prepreg or the 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 obtained laminate are highly balanced, which is preferable.

The thickness of the prepreg according to this 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 shapeability during lamination and the properties such as 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 is excellent in dielectric properties, heat resistance, mechanical properties, etc., and thus can be suitably used for a circuit board.
As a method for producing the circuit board, a generally known method can be adopted and is not particularly limited. For example, the film, sheet or prepreg produced by the above method is heat-cured by a laminating press or the like to form an electric insulating layer. Next, a conductor layer is laminated on the obtained electric insulating layer by a known method to produce a laminated body. Then, a circuit board can be obtained by subjecting the conductor layer in the laminated body to circuit processing or the like.

As the metal forming the conductor layer, a metal such as copper, aluminum, nickel, gold, silver and stainless can be used. As a method of forming the conductor layer, for example, a method of heat-bonding the metal or the like to a foil or the like on the electric insulation layer, or a method of laminating the metal or the like to the electric insulation layer using an adhesive agent Alternatively, a method of forming a conductor layer made of the metal on the electric insulating layer by a method such as sputtering, vapor deposition, plating or the like can be used. The circuit board may be either a single-sided plate or a double-sided plate.

Such a circuit board can be used as an electronic device by mounting an electronic component such as a semiconductor element, for example. The electronic device can be manufactured based on known information.
Examples of such electronic devices include ICT infrastructure devices such as servers, routers, supercomputers, mainframes, workstations; antennas such as GPS antennas, antennas for radio base stations, millimeter wave antennas, RFID antennas; mobile phones. , Smartphones, PHS, PDAs, tablet terminals and other communication devices; personal computers, TVs, digital cameras, digital video cameras, POS terminals, wearable terminals, digital media players and other digital devices; electronic control system devices, in-vehicle communication devices, cars In-vehicle electronic equipment such as navigation equipment, millimeter-wave radar, in-vehicle camera module, etc.; semiconductor test equipment, high-frequency measuring equipment, etc.

[Foam]
Further, the cyclic olefin-based copolymer composition according to the present embodiment can be made into a foam by crosslinking and foaming. At this time, the above-mentioned foaming agent may be added to the cyclic olefin-based copolymer composition.

[Use]
Since the cyclic olefin-based copolymer (m), the cyclic olefin-based copolymer composition and the crosslinked product (Q) according to this embodiment are excellent in solvent resistance, heat resistance, mechanical strength and transparency, The molded body made of a body is, for example, an optical fiber, an optical waveguide, an optical disk substrate, an optical filter, a lens, an adhesive for optics, an optical filter for PDP, a coating material for organic EL, a base film base material for a solar cell in the aerospace field, and a sun. 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 for forming insulating layers of circuit boards, and display parts Overcoat materials or interlayer insulating materials, such as liquid crystal displays and solar cell substrates, medical equipment, automotive parts, release agents, resin modifiers, transparent substrates for displays, lithium ion battery parts, semiconductor process parts, Film capacitors, gas barrier coating materials, wire coating materials, automotive materials, aerospace materials, semiconductor process materials, wire coating materials, lithium ion battery materials, fuel cell materials, capacitor films, flexible display materials, anchor coating materials , Transparent adhesives, modifiers, crosslinking aids, medical containers, medical catheter members, waterproof sealing materials, mold release materials, hard coat materials, foam modifiers.
In particular, it has excellent stability over time in dielectric properties, solvent resistance, heat resistance, transparency, mechanical properties, etc., and thus can be suitably used for high-frequency applications such as high-frequency circuit boards. Furthermore, since it has excellent gas barrier properties, it can be suitably used as a substrate, a film or a sheet of a liquid crystal display or a solar cell.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.

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

The composition of the cyclic olefin-based copolymer (m) used in Synthesis Examples, Examples, and Comparative Examples was measured for intrinsic viscosity [η] by the method described below.

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

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

Further, the molecular weight of the cyclic olefin-based copolymer (m) used in Synthesis Examples, Examples and Comparative Examples was measured by the method described below.

<Number average molecular weight (Mn)>
The number average molecular weight (Mn) of the cyclic olefin-based copolymer (m) was measured by GPC measurement and determined as a standard polystyrene conversion value. The GPC measurement was performed under the following conditions.
Device: GPC HLC-8321 (Tosoh Corporation)
Solvent: o-dichlorobenzene Column: TSKgel GMH6-HTx2, TSKgel GMH6-HTLx2 (all manufactured by Tosoh Corporation)
Flow rate: 1.0 ml/min Sample: 1 mg/mL o-dichlorobenzene solution Temperature: 140°C

The molded products (films) obtained in Examples and Comparative Examples were evaluated by the method described below.

Dielectric loss tangent evaluation: Dielectric loss tangent at 10 GHz was evaluated for the films obtained in Examples and Comparative Examples by the cylindrical cavity method.

Tg measurement: Solid viscoelastic temperature dispersion measurement of the obtained film was performed, and the peak temperature of tan δ was taken as Tg. The measurement was performed under the following conditions.
Device: RSA-III (manufactured by TA Instruments)
Deformation mode: Tensile heating rate: 3°C/min Frequency: 1Hz
Setting distortion: 0.1%
Environment: under nitrogen

The following raw materials were used in the experiment.

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

MMAO (manufactured by Tosoh Finechem)
Toluene (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)
5-Vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (manufactured by Mitsui Chemicals, Inc.)
Acetone (Wako Pure Chemical Industries, Ltd.: Wako special grade)
Methanol (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

Radical polymerization initiator:
Cross-linking agent 1: Park Mill D (manufactured by NOF CORPORATION)
silica:
Silica 1: SFP-30M (manufactured by Denka)
Flame retardants:
Flame retardant 1: SAYTEX BT93 (manufactured by Albemarle)
Antioxidant Antioxidant 1: Irganox 1010 (manufactured by BASF)
Glass cloth:
Glass cloth 1: 1013NT-S640 (manufactured by Arisawa Seisakusho)

Cyclic olefin copolymer (m):
[Synthesis Example 1 (Cyclic Olefin Copolymer (m-1) (Mn = 11,900))]
In a SUS autoclave having an internal volume of 1 L that was sufficiently replaced with nitrogen, toluene 380 mL, 5-vinyl-2-norbornene (hereinafter, also referred to as VNB) 94 mL, tetracyclo[4.4.0.1 ^2,5 . 26 mL of 1 ^7,10 ]-3-dodecene (hereinafter, also referred to as TD), a toluene solution of MMAO (manufactured by Tosoh Finechem Co., Ltd.), 1.5 mmol in terms of Al, and 868 mL of hydrogen were inserted, and then ethylene was added to the system. It was introduced until the pressure reached 0.78 MPaG. After adding 33 μmol of the transition metal compound (1) dissolved in toluene and conducting polymerization at 35° C. for 180 minutes, the obtained polymer solution was added with acetone/methanol (=3/3) containing 0.1 vol% concentrated hydrochloric acid. 1) The mixture was poured into a mixed solvent to precipitate a polymer, which was stirred and then filtered with filter paper. The obtained solid was dried under reduced pressure at 80° C. for 10 hours to obtain an ethylene (denoted by E in the table)/TD/VNB copolymer. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 35.9 mol %, the composition ratio of the TD-derived structure was 6.5 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,900. It was The intrinsic viscosity [η] was 0.08 dl/g.

[Synthesis Example 2 (Cyclic Olefin Copolymer (m-2) (Mn = 11,900)]]
An ethylene/TD/VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that 376 mL of toluene, 90 mL of VNB, 34 mL of TD, and 744 mL of hydrogen were used.
The composition ratio of the VNB-derived structure in the polymer determined by NMR was 33.4 mol %, the composition ratio of the TD-derived structure was 9.6 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,900. It was The intrinsic viscosity [η] was 0.07 dl/g.

[Synthesis Example 3 (Cyclic Olefin Copolymer (m-3) (Mn = 11,300))]
An ethylene/TD/VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that toluene was 378 mL, VNB was 79 mL, TD was 43 mL, and hydrogen was 744 mL. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 29.9 mol %, the composition ratio of the TD-derived structure was 13.1 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,300. It was The intrinsic viscosity [η] was 0.04 dl/g.

[Synthesis Example 4 (Cyclic Olefin Copolymer (m-4) (Mn=10,500))]
An ethylene/TD/VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that 377 mL of toluene, 73 mL of VNB, 50 mL of TD, and 744 mL of hydrogen were used. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 27.7 mol %, the composition ratio of the TD-derived structure was 15.0 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 10,500. It was The intrinsic viscosity [η] was 0.07 dl/g.

[Synthesis Example 5 (Cyclic Olefin Copolymer (m-5) (Mn = 11,600))]
An ethylene/TD/VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that 418 mL of toluene, 65.0 mL of VNB, 17.5 mL of TD, and 1339 mL of hydrogen were used. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 33.2 mol %, the composition ratio of the TD-derived structure was 5.9 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,600. It was

[Synthesis Example 6 (Cyclic Olefin Copolymer (m-6) (Mn 14,900))]
An ethylene/TD/VNB copolymer was obtained in the same manner as in Synthesis Example 1 except that 447 mL of toluene, 45.3 mL of VNB, 8.2 mL of TD, and 1339 mL of hydrogen were used. The composition ratio of the VNB-derived structure in the polymer determined by NMR was 32.7 mol %, the composition ratio of the TD-derived structure was 3.9 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 14,900. It was

[Example 1]
(Preparation of varnish 1)
The cyclic olefin-based copolymer (m-1) obtained in Synthesis Example 1, a cross-linking agent 1 as a radical polymerization (cross-linking) initiator (Perky Mill D manufactured by NOF CORPORATION), and an antioxidant 1 (BASF) as an antioxidant. Irganox 1010 manufactured by Co., Ltd.), toluene was used as a solvent, and the composition was weighed according to the composition of Table 1. The weighed sample was placed in a 200 mL separable flask, and stirred with a stirring blade at a rotation speed of 200 rpm for 4 hours until it was sufficiently dissolved, to obtain a target varnished cyclic olefin-based copolymer composition. .. The unit of the mixing ratio of each raw material in Table 1 is parts by mass.

(Film formation)
The resulting varnished cyclic olefin-based copolymer composition was applied onto a release-treated PET film at a speed of 10 mm/sec, and then in a blower dryer under a nitrogen stream at 150° C. for 4 minutes. Dried. 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. Dielectric loss tangent measurement and Tg measurement were performed on the obtained laminated film. The results obtained are shown in Table 1.

[Examples 2-5 and Comparative Examples 1-2]
Films were prepared and evaluated in the same manner as in Example 1 except that the compounding composition shown in Table 1 was used. The results obtained are shown in Table 1.

[Example 6]
A prepreg and its laminate were prepared by the following method, and solder heat resistance was evaluated.

(Preparation of crosslinkable resin composition (P-1) varnish)
42 parts of cyclic olefin copolymer (m-1), 28 parts of silica (manufactured by Denka, SFP-30M), 30 parts of flame retardant (manufactured by Albemarle, SAYTEX BT93), antioxidant (manufactured by BASF, Irganox 1010) 0. A varnish-like crosslinkable resin composition (P-1) was prepared by adding to the toluene at a ratio of 0.024 parts by weight and 0.88 parts by weight of a crosslinking agent (Parkmill D, manufactured by NOF CORPORATION) and mixing them.

(Preparation of resin fiber composite layer (Q))
The varnish-like crosslinkable resin composition (P-1) thus obtained was impregnated into glass cloth (Arisawa Seisakusho Co., Ltd., 1031NT S640) and dried at 125° C. for 150 seconds in a blast dryer to obtain a prepreg (Q -1) was produced.

(Preparation of laminated body)
Four prepregs (Q-1) were laminated, both sides were sandwiched with copper foil (F1-WS, manufactured by Furukawa Electric Co., Ltd.), and 3 MPa was applied by a vacuum press to raise the temperature from room temperature (25° C.) at a constant rate. Then, it was held at 180° C. for 120 minutes to obtain a copper clad laminate. A solder heat resistance test was performed on the obtained copper clad laminate.

[Solder heat resistance test]
The copper foil on one surface of the obtained copper-clad laminate was etched, and the test piece treated for 120 minutes at 121° C. and 100% RH atmosphere was immersed in solder at 288° C. for 3 minutes to evaluate the solder heat resistance. .. As a result of the evaluation, no abnormality such as swelling of the copper foil was observed, and it was judged that the obtained copper-clad laminate had excellent solder heat resistance.

Claims (12)

A repeating unit (A) derived from at least one olefin represented by the following general formula (I):
A repeating unit (B) derived from one or more cyclic non-conjugated dienes represented by the following general formula (III),
A cyclic olefin-based copolymer (m) comprising one or more cyclic olefin-derived repeating units (C) represented by the following general formula (V):
When the total number of moles of repeating units in the cyclic olefin-based copolymer is 100 mol %,
A cyclic olefin in which the total 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 in the range of 40.0 mol% or more and 50.0 mol% or less. Type copolymer.

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

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

[In the general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same as each other. They may be different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 to 6 carbon atoms. 20 is an aromatic hydrocarbon group, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. ] The cyclic olefin-based copolymer according to claim 1, wherein the content of the repeating unit (C) derived from the cyclic olefin is 1.0 mol% or more and 16.0 mol% or less. The cyclic olefin-based copolymer according to claim 1 or 2, which has a number average molecular weight Mn of 3,000 or more and 30,000 or less. The cyclic olefin-based copolymer according to any one of claims 1 to 3,
The cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the cyclic olefin-derived repeating unit (C) is tetracyclo[4. 4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene-containing cyclic olefin-based copolymer. A cyclic olefin-based copolymer composition comprising the cyclic olefin-based copolymer (m) according to any one of claims 1 to 4. A varnish containing the cyclic olefin-based copolymer composition according to claim 5 and a solvent. A crosslinked product obtained by crosslinking the cyclic olefin-based copolymer composition according to claim 5. A film or sheet comprising the crosslinked product according to claim 7. A laminate comprising the crosslinked product according to claim 7. A circuit board comprising: an electrically insulating layer containing the crosslinked body according to claim 7; and a conductor layer provided on the electrically insulating layer. An electronic device comprising the circuit board according to claim 10. A prepreg comprising the cyclic olefin-based copolymer composition according to claim 5 and a sheet-shaped fiber base material.