WO2000012586A1 - Norbornene copolymer produced by ring-opening polymerization - Google Patents

Abstract

A norbornene copolymer produced by ring-opening polymerization which comprises repeating units [A] and [B] derived from at least two norbornene compounds containing no substituents and repeating units [C] derived from a norbornene compound which is composed of at least four rings and has at least one C1-4 substituent; and a process for producing the copolymer.

Description

 g Tsukiitoda Norbornene-based ring-opening copolymer Technical field to which the invention pertains

 The present invention relates to a novel norbornene-based ring-opening copolymer, a hydrogenated product thereof, and a method for producing the same. More specifically, the present invention relates to optical properties such as transparency and low birefringence; Without deteriorating various properties such as weather resistance properties such as water absorption; electrical properties such as low dielectric constant and low dielectric loss tangent; chemical properties such as solvent resistance and heat deterioration resistance; and mechanical properties such as impact strength and hardness. A norbornene-based ring-opening copolymer which can be produced with high productivity by improving the solution stability after the polymerization reaction or the hydrogenation reaction to reduce the restrictions on polymer production, and its hydrogenated product, and It relates to a method for producing them. Background art

 Thermoplastic norbornene resins have optical properties such as transparency and low birefringence; weather resistance properties such as moisture resistance, heat resistance and low water absorption; electrical properties such as low dielectric constant and low dielectric loss tangent; solvent resistance and heat resistance. Due to its excellent properties, such as chemical properties such as deterioration, and mechanical properties such as impact strength and hardness, applications in various application fields are being studied.

 In recent years, it has been reported that a hydrogenated ring-opening copolymer composed of a disc-opened pentadiene-based monomer and a tetracyclododecene-based monomer has excellent heat resistance, optical properties, moldability, moisture resistance, etc. (For example, JP-A-64-248826, JP-A-11-38257, JP-A-1-68752, JP-A-Heisei 2 — See Japanese Patent Publication No. 1022221). These hydrogenated binary norbornene ring-opening copolymers undergo polymerization and hydrogenation in a solution heated to a predetermined reaction temperature.

However, when only the dicyclic pentagen having no substituent and tetracyclododecene are combined, if the solution after the above polymerization reaction or after the hydrogenation reaction is stored at room temperature, it is dissolved in the solution in a short time. The resulting polymer tends to precipitate and solidify, making it difficult to store in solution for long periods of time. For this reason, there is a major restriction in production that the solution after the polymerization reaction or the hydrogenation reaction must be promptly transferred to the concentration step. In addition, when the solution after the above polymerization reaction or after the hydrogenation reaction is stored at room temperature for a long period of time, a separate step of dissolving the precipitated and solidified polymer is required before proceeding to the concentration step. It is considered to be an obstacle.

 Therefore, the solution after the polymerization reaction or after the hydrogenation reaction can be stored at room temperature for a long time without deteriorating various properties such as the optical properties, weather resistance, electrical properties, chemical properties, and mechanical properties of the resulting polymer. Even so, there is a need for a hydrogenated norbornene ring-opening copolymer having improved solution stability after the reaction such that the resulting polymer does not precipitate and solidify. Disclosure of the invention

 An object of the present invention is to solve the problems of the prior art and to reduce the properties of the resulting polymer such as optical properties, weather resistance, electrical properties, chemical properties, mechanical properties, etc. A norbornene-based ring-opening copolymer, a hydrogenated product thereof, and a method for producing the same that can be produced with high productivity by improving the solution stability after the addition reaction and reducing the restrictions on polymer production. To provide.

 The present inventors have conducted intensive studies to achieve the above object.As a result, at least two types of norbornenes having a specific substituent have been added to at least two types of norbornenes having a specific substituent. Ring-opening polymerization of a norbornene-based monomer to which is added, after the polymerization reaction or hydrogen without deteriorating various properties such as optical properties, weather resistance properties, electrical properties, chemical properties, and mechanical properties of the resulting polymer They have found that the solution stability after the addition reaction can be improved, and have completed the present invention.

 (1) The “norbornene-based ring-opening copolymer” according to the present invention comprises one or more repeating units [A] and [B] derived from at least two types of norbornenes having no substituent. And a repeating unit [C] derived from four or more norbornenes having at least one substituent having four or less carbon atoms.

The norbornene-based ring-opening copolymer is preferably hydrogenated to obtain a hydrogenated norbornene-based ring-opening copolymer. The degree of hydrogenation is particularly But not limited to, the proportion of the repeating unit having a carbon one-carbon double bonds in the main chain structure of the norbornene-based ring-opening copolymer is preferably 20 mol% or less, more rather preferably 5 mol ⁰ / o or less More preferably, hydrogenation is carried out so as to be 2 mol% or less. The number average molecular weight (Mn) of the norbornene-based ring-opening copolymer and its hydrogenated product is not particularly limited, but is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, and preferably 500,000 or more. Hereinafter, it is more preferably 200,000 or less, further preferably 100,000 or less. In the norbornene-based ring-opening copolymer and its hydrogenated product, it is derived from at least two types of norbornenes having no substituent in all repeating units [A], [B] and [C]. Although the content ratio of the repeating units [A] and [B] is not particularly limited, it is preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 50% by weight or more, and preferably 90% by weight or more. % By weight, more preferably not more than 85% by weight, even more preferably not more than 80% by weight. Further, in the norbornene-based ring-opening copolymer or its hydrogenated product, a tetracyclic having at least one specific substituent in all repeating units [A], [B] and [C] The content ratio of the repeating unit [C] derived from the norbornenes is not particularly limited, but is preferably 10% by weight or more, more preferably 15% by weight or more, and further preferably 20% by weight or more. Preferably, it is at most 70% by weight, more preferably at most 60% by weight, even more preferably at most 50% by weight.

 Of the repeating units [A] and [B] derived from at least two types of norbornenes having no substituent, [A] is selected from tetracyclic or more norbornenes having no substituent. It is preferred that [B] is a repeating unit derived from a bicyclic or tricyclic norbornene having no substitution.

The content of [A] in the repeating units [A] and [B] derived from at least two types of norbornenes having no substituent is preferably 5% by weight or more, more preferably 1% by weight or more. 0 wt% or more, more preferably a 20% by weight or more, good Mashiku 95 wt% or less, more preferably 90 wt% or less, more preferably 8 0 weight ⁰ /. And at least two types of norbornene having no substituent The content of [B] in the repeating units [A] and [B] derived from the compounds is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% by weight or more. It is preferably at most 95% by weight, more preferably at most 90% by weight, even more preferably at most 80% by weight.

 (2) The “process for producing a norbornene-based ring-opening copolymer” according to the present invention comprises: at least two types of norbornenes [] ′] and [Β ′] having no substituent; A ring-opening polymerization of a norbornene-based monomer containing a tetracyclic or more norbornene [C ′] having at least one substituent having at least one carbon atom in the presence of a metathesis polymerization catalyst; and Hydrogenating 80% or more, preferably 95% or more, more preferably 98% or more of the carbon-carbon double bonds in the main chain structure of the obtained ring-opened polymer.

 The content ratio of at least two types of norbornenes having no substituent [Α ′] and [Β ′] in the norbornene-based monomer is not particularly limited, but is preferably 30% by weight or more, more preferably Is 40% by weight or more, more preferably 50% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, and further preferably 80% by weight or less. The content ratio of the norbornene [C '] having four or more rings having at least one specific substituent in the norbornene-based monomer is not particularly limited, but is preferably 10% by weight. It is at least 15% by weight, more preferably at least 20% by weight, preferably at most 70% by weight, more preferably at most 60% by weight, even more preferably at most 50% by weight.

 Of the at least two types of norbornenes having no substituent [Α '] and [Β'], preferred are [好 ま し く '], and four or more norbornenes having no substituent, preferably [ Β '] is a bicyclic or tricyclic norbornene having no substituent.

The content ratio of [Α '] in at least two types of norbornenes having no substituents [Α'] and [Β '] is not particularly limited, but is preferably 5% by weight or more, more preferably 1% by weight or more. 0% by weight or more, more preferably 20% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, further preferably 80% by weight or less. % By weight or less.

The content ratio of [Β '] in at least two types of norbornenes [Α'] and [Β '] having no substituent is not particularly limited, but is preferably 5% by weight or more, more preferably Is 10% by weight or more, more preferably 20% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, and further preferably 80% by weight. / ₀ or less.

 Action

 The norbornene-based ring-opening copolymer according to the present invention comprises a repeating unit derived from at least two types of norbornenes having no substituent, and a tetracyclic or more norbornene having at least one type of specific substituent. Since it is composed of derived repeating units, it does not deteriorate the optical properties, weather resistance, electrical properties, chemical properties, mechanical properties, etc. of the resulting polymer, after polymerization reaction or hydrogenation Even if the solution after the reaction is stored at room temperature for a long period of time, it is possible to prevent inconvenience caused by precipitation and solidification of the produced polymer. Therefore, the solution after the reaction can be stored stably for a long period of time (excellent in solution stability after the reaction), so that the restriction on the production of the polymer is reduced, and a separate process for dissolving the precipitated and solidified polymer is also required. Since it is not necessary to provide such a polymer, it is possible to produce a polymer with high productivity.

 By further hydrogenating the norbornene-based ring-opening copolymer according to the present invention to obtain a hydrogenated norbornene-based ring-opening copolymer, the optical properties, oxidation-deterioration resistance, light-resistance, and electrical insulation are particularly improved. Properties can be improved. In particular, by reducing the proportion of the repeating unit having a carbon-carbon double bond in the main chain structure of the norbornene-based ring-opening copolymer according to the present invention to preferably 20 mol% or less, the optical properties can be improved. Various properties such as oxidation resistance, light resistance, and electrical insulation can be further improved.

 By setting the number average molecular weight (Μ η) of the norbornene-based ring-opening copolymer and the hydrogenated product thereof according to the present invention to preferably 500 to 50,000, mechanical strength and moldability are improved. And the balance between them can be excellent.

In the norbornene-based ring-opening copolymer and the hydrogenated product thereof according to the present invention, at least one of the repeating units [A], [Β] and [C] having no substituent The content ratio of the repeating units [A] and [B] derived from two kinds of norbornenes is preferably 30% by weight or more and 90% by weight or less, and a 4-ring having at least one type of specific substituent. By adjusting the content of the repeating unit [C] derived from the norbornene compound in a form of at least 10% by weight to at most 70% by weight, the norbornene-based ring-opening copolymer and its hydrogenated product can be obtained. Without compromising the optical, weathering, electrical, chemical, and mechanical properties of the resulting polymer, in particular, a high balance between solution stability after the reaction and solvent resistance of the resulting polymer. Can be. Of the repeating units [A] and [B] derived from at least two types of norbornenes having no substituent, [A] is derived from a tetracyclic or more norbornene having no substituted group By using such a repeating unit, mechanical strength and heat resistance can be improved. In addition, among the repeating units [A] and [B] derived from at least two types of norbornenes having no substituent, [B] is a bicyclic or tricyclic norbornene having no substitution. By using a repeating unit derived from the above, it is possible to improve not only mechanical strength and melt stability but also impact resistance.

Repeating units of which are derived from at least two norbornene no substituents in the [A] and [B], the content ratio of [A], preferably 5 wt _^0/0 to 9 5 wt% or less By setting the content ratio of [B] to preferably 5% by weight or more and 95% by weight or less, mechanical strength, melt stability and heat resistance can be highly balanced.

According to the method for producing a norbornene-based ring-opening copolymer according to the present invention, at least two types of norbornenes having no substituent and four or more types of norbornenes having at least one specific substituent are provided. Since it contains a norbornene-based monomer, it does not degrade the optical, weather, electrical, chemical, and mechanical properties of the resulting polymer, after polymerization or hydrogenation. Even if the subsequent solution is stored at room temperature for a long period of time, the hydrogenated product of the norbornene-based ring-opening copolymer can be obtained by preventing the inconvenience caused by precipitation and solidification of the produced polymer. Therefore, the solution after the reaction can be stably stored for a long period of time (excellent in solution stability after the reaction), which reduces restrictions on the production of the polymer, and requires a separate dissolution step for the precipitated polymer. Gana Therefore, the polymer can be produced with high productivity.

 Further, according to the method for producing a norbornene-based ring-opening copolymer according to the present invention, hydrogen is added so that the proportion of the repeating unit having a carbon-carbon double bond in the main chain structure is at least 20 mol% or less. Since it is added, it is possible to obtain a hydrogenated norbornene-based ring-opening copolymer excellent in oxidation deterioration resistance, weather deterioration resistance and light deterioration resistance.

 The norbornene-based monomer used in the method for producing a norbornene-based ring-opening copolymer according to the present invention contains at least two unsubstituted norbornenes [Α ′] and [Β ′]. The ratio is preferably 30% by weight or more and 90% by weight or less, and the content ratio of the norbornenes [C ′] of four or more rings having at least one specific substituent is preferably 10% by weight. By setting the content to 70% by weight or less, the resulting norbornene-based ring-opened copolymer has mechanical strength, excellent melt stability and heat resistance, and furthermore has the optical properties, weather resistance, and electrical properties of the resulting polymer. To obtain a hydrogenated norbornene ring-opening copolymer that does not degrade various properties such as properties, chemical properties, and mechanical properties, and that has a particularly high balance between solution stability after the reaction and solvent resistance of the formed polymer. Can be. Among at least two types of norbornenes [Α '] and [Β'] having no substituent, by making [Α '] a four- or more-ring norbornene having no substituent, A hydrogenated norbornene-based ring-opening copolymer having excellent mechanical strength and heat resistance can be obtained. In addition, at least two types of norbornenes having no substituent

Of [Α '] and [Β'], by setting [Β '] to a bicyclic or tricyclic norbornene having no substituent, it has high mechanical strength and melt stability as well as shock resistance. A hydrogenated norbornene-based ring-opening copolymer having excellent properties can be obtained. The content ratio of [Α '] in at least two types of norbornenes having no substituents [['] and [Β '] is preferably 5% by weight or more and 95% by weight or less; By controlling the content ratio of 5% by weight or more to 95% by weight or less, it is possible to obtain a hydrogenated norbornene-based ring-opening copolymer having a highly balanced mechanical strength, melt stability, and heat resistance. Can be.

Best mode for carrying out the invention. Hereinafter, the norbornene-based ring-opening copolymer according to the present invention, hydrogenated products thereof, and methods for producing them will be described based on the following embodiments. However, these embodiments are described for facilitating the understanding of the present invention, and are not described for limiting the present invention.

 In the present invention, “norbornenes” mean a monomer having a norbornene ring. “Norbornene-based monomer” means a monomer having a monomer having a norbornene ring structure in the molecule as a main component. Further, a monomer having n hydrocarbon rings in the molecule is referred to as an “n-ring monomer”.

 Norbornene ring-opening copolymer hydrogenated product

 The hydrogenated norbornene-based ring-opening copolymer according to the present invention comprises repeating units [A] and [B] derived from two types of norbornenes having no substituents, and 1 to 4 carbon atoms. And a repeating unit [C] derived from four or more norbornenes having at least one substituent having an atom.

 (1) Repeating units derived from two unsubstituted norbornenes [A] and [B]

 The repeating units [A] and [B] derived from the first and second norbornenes constituting the hydrogenated norbornene ring-opening copolymer according to the present invention have no substituents. Such a repeating unit is not particularly limited. For example, [A] can be represented by the following formula (A 1). However, a in the following formula (A 1) is 0, 1 or 2. · · · · Is a carbon-carbon single bond or a double bond.

繰り返し単位 [A] の好ましい態様としては、 たとえば、 下記式 （A2) で表 わされる繰り返し単位を挙げることができる。 ただし、 下記式 （A2) 中の · · • ·は、 炭素一炭素単結合または二重結合である。

Preferred embodiments of the repeating unit [A] include, for example, a repeating unit represented by the following formula (A2). However, in the following formula (A2), · · · · is a carbon-carbon single bond or a double bond.

また、 [B] としては、 下記式 （B 1) およびノまたは （B 2) で表わすこと ができる。 ただし、 下記式 （B 1) 中の bは 0、 1または 2である。 … …は、 炭素—炭素単結合または二重結合である。 また、 下記式 （B 2) 中の · · · ·は、 炭素一炭素単結合または二重結合である。

[B] can be represented by the following formula (B1) and (B) or (B2). However, b in the following formula (B1) is 0, 1 or 2. ... is a carbon-carbon single bond or a double bond. Also, in the following formula (B 2), ····· is a carbon-carbon single bond or a double bond.

本発明に係るノルボルネン系開環共重合体水素添加物を構成する置換基を有さ ないノルボルネン類から誘導される繰り返し単位 [A] および [B] として、 上 述の単位を広く用いることができるが、 特に、 好ましくは、 [A] が 4環体以上 のノルボルネン類から誘導される繰り返し単位であり、 [B] が 2環体若しくは 3環体のノルボルネン類から誘導される繰り返し単位である。 (B 2)

As the repeating units [A] and [B] derived from unsubstituted norbornenes constituting the hydrogenated norbornene-based ring-opening copolymer according to the present invention, the above-mentioned units can be widely used. In particular, [A] is a repeating unit derived from a norbornene having four or more rings, and [B] is a repeating unit derived from a norbornene having two or three rings.

 (2) Repeating units derived from four or more norbornenes having at least one specific substituent [C]

 The repeating unit [C] derived from the third norbornene constituting the hydrogenated norbornene-based ring-opening copolymer according to the present invention is a repeating unit derived from the first and second norbornenes. Unlike [A] and [B], it has a specific substituent, that is, at least one substituent having 1 to 4 carbon atoms. Such a repeating unit can be represented by the following formula (C1).

ただし、 上記式 （C 1) 中の各記号の意味は、 次のとおりである。

However, the meaning of each symbol in the above formula (C1) is as follows.

 c is 1 or 2.

R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an alkoxycarbonyl group, an acyloxy group, an alkoxy group, a cyano group, an amide group, an imido group, a silyl group, or The hydrocarbon group can be a hydrocarbon group substituted by a polar group (halogen atom, hydroxyl group, alkoxycarbonyl group, acyloxy group, alkoxy group, cyano group, amide group, imido group, or silyl group). In other words, at least ^{one of} R ^{1 to} R ⁴ needs to be at least one substituent having 1 or more and 4 or less carbon atoms. The halogen atom in the formula (C1) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Can be

Two or more of R ^{1 to} R ⁴ may combine with each other to form an alkenyl group having 4 carbon atoms, or R ¹ and R ² , or R ³ and R ⁴ An alkylidene group may be formed.

 ... is a carbon-carbon single bond or a double bond.

 Examples of the hydrocarbon group include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 4 carbon atoms, and a cycloalkyl group having 3 to 4 carbon atoms.

 Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 4 carbon atoms.

 A hydrocarbon group that is not substituted with a polar group is suitable for applications requiring low water absorption.

 Preferred as at least one substituent having 1 to 4 carbon atoms are, for example, methyl, ethyl, propyl, i-propyl, n-butyl, 1-methylpropyl, 2 —A linear or branched “alkyl group” such as a methylpropyl group; a “cycloalkyl group” such as a cyclopropyl group and a cyclobutyl group; an “alkylidene group” such as a methylidene group, an ethylidene group, and a propylidene group; "Alkylene group" such as propane-1,3-diyl group, butane-1,4-diyl group; methoxy group, ethoxy group, propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, “Alkoxy groups” such as t-butoxy groups; “Alkoxy groups” such as methoxycarbonyl groups, ethoxycarbonyl groups, and propoxycarbonyl groups A "rubonyl group"; an "acyloxy group" such as an acetyloxy group and a propanoyloxy group; a "silyl group" such as a trimethylsilyl group; More preferred are an alkyl group, a cycloalkyl group, an alkylidene group, an alkylene group, and an alkoxy group.

 Particularly preferred are an alkyl group and an alkylidene group.

本発明に係るノルボルネン系開環共重合体水素添加物が、 極性基含有の繰り返 し単位を有する場合、 その含有比率は、 特に限定はなく使用目的に応じて適宜選 択されるが、 吸湿による変形やクラックの発生を極度に抑制することが要求され る用途においては、 ノルボルネン系開環共重合体水素添加物中の通常 30重量⁰ /。 以下、 好ましくは 1 0重量％以下、 より好ましくは 5重量％以下の割合とするこ とが望ましい。 Preferred examples of the above formula (C 1) include the following formula (C 1-1). However, R ¹ to R ⁴ of formula (CI- 1) in is the same as R ¹ to R ⁴ in the formula (C 1).

When the hydrogenated norbornene ring-opening copolymer according to the present invention has a repeating unit containing a polar group, the content ratio is not particularly limited and may be appropriately selected depending on the purpose of use. in extremely suppressed it Ru is required to use the occurrence of deformation and cracks due to the normal 30 wt norbornene ring-opening polymer hydride in ⁰ /. Below, it is desirable to set the ratio to preferably 10% by weight or less, more preferably 5% by weight or less.

 The number average molecular weight (Mn) of the hydrogenated norbornene-based ring-opening copolymer according to the present invention is determined by gel permeation using cyclohexane (or another solvent such as toluene as appropriate if not soluble in cyclohexane) as a solvent. It is measured by the Chromatography-One (GPC) method and is expressed in terms of polyisoprene.

 The molecular weight distribution of the hydrogenated norbornene-based ring-opening copolymer of the present invention is appropriately selected according to the purpose of use, but the weight average molecular weight based on the number average molecular weight (Mn) in terms of polyisoprene measured by the GPC method. When the ratio (MwZMn) of (Mw) is usually 5 or less, preferably 4 or less, and more preferably 3 or less, mechanical strength and formability are highly balanced and suitable.

 The glass transition temperature (T g) of the hydrogenated norbornene ring-opening copolymer of the present invention may be appropriately selected depending on the purpose of use, and is usually from 110 ° C. to 250 ° C. . From the viewpoint of heat resistance, Tg is desirably high, and is usually 70 ° C or higher, preferably 90 ° C or higher, and more preferably 110 ° C or higher.

 'Production method of hydrogenated ring-opening copolymer

The method for producing the hydrogenated norbornene ring-opening copolymer according to the present invention is not particularly limited. For example, two types of norbornenes having no substituent [Α ′] and A norbornene-based monomer containing [Β '] and a tetracyclic or more norbornene [C'] having at least one substituent having at least 1 and no more than 4 carbon atoms is subjected to metathesis polymerization. A production method comprising a step of carrying out ring-opening polymerization in the presence of a catalyst and a step of hydrogenating at least 80% of carbon-carbon double bonds in the main chain structure of the obtained ring-opened polymer. it can.

 (1) Two types of norbornenes having no substituents [Α ′] and [Β ′] First and second norbornenes used in the method for producing a hydrogenated norbornene-based ring-opening copolymer according to the present invention The classes [Α '.] And [Β'] both have no substituents. Such norbornenes are not particularly limited. For example, the first norbornene [Α ′] can be represented by the following formula (Α ′ 1). However, the meanings of the symbols in the following formula (Α'1) are the same as those in the above formula (A1).

A preferred embodiment of the norbornenes represented by the above formula (Α'1) is represented by the following formula (Α'2).

F and n are represented by the formulas (Α '1) or (Α' 2). These can be used alone or in combination of two or more.

 The second norbornene [Β '] can be represented by, for example, the following formula (Β'1). However, the meaning of each symbol in the following formula (Β ′ 1) is the same as that in the above formula (Β1).

A preferred embodiment of the norbornenes represented by the above formula (Β'1) is represented by, for example, the following formula (た と え ば '2).

Further, another preferred embodiment of the norbornenes represented by the above formula (Β′1) is represented by, for example, the following formula (Β′3).

これらの式 （Β' 1) 〜 （Β' 3) で表されるノルボルネン類は、 それぞれ単 独で、 あるいは 2種以上組み合わせて用いることができる。

The norbornenes represented by these formulas (Β ′ 1) to (Β ′ 3) can be used alone or in combination of two or more.

 The norbornenes described above can be widely used as the two non-substituted norbornenes [Α ′] and [Β ′] used in the method of the present invention. ] Is preferably a tetracyclic or more norbornene, and [Β '] is preferably a bicyclic or tricyclic norbornene.

 The norbornenes having four or more rings are not particularly limited, but those having no substituent are used in the present invention. Specifically, for example, tetracyclo

^{[4. 4. 0. I 2 '5} . I 7' 10] Dodeka 3- E emissions (intends simply Rere both tetracyclododecene), to Kisashikuro ^{[6. 6. 1. I 3 '6} . 1 10' ^{13.0 2, 7.} 0 ^{9 '14]} such heptadec _ 4 E emissions and the like.

 Among these tetracyclic or more norbornenes, tetracyclide dodecene is particularly preferred in view of industrial availability of the monomer and excellent balance of impact resistance, moldability and heat resistance.

 As bicyclic norbornenes, bicyclo [2.2.1] hepta-1-ene (common name norbornene) is used.

The tricyclic norbornenes include tricyclo [4.3.0. I ² ' ⁵ ] deca-3,7-gen (common name dicyclopentagen), which is a dimer of cyclopentene pentagen. moiety is a hydrogenated product (or an adduct of cyclopentadiene and cyclopentene) tricyclo [4.3.1 0.1 ^{2 '5]} Deka 3 E emissions; cyclopenta Jen is the adduct of Kisajen cyclohexylene tricyclo [4 4. 0. I ² ' ⁵ ] force _ 3,7-gen or tricyclo [4. 4.0.1. ² ' ⁵ ] force -3,8-gen, or a partial hydrogenated product thereof (or An adduct of cyclopentadiene and cyclohexene) such as tricyclo [4. 4. 0. I ² ' ⁵ ]

These bicyclic or tricyclic norbornenes can be used alone or in combination of two or more. Is not particularly limited constant compounding ratio when combined, preferably, the amount of norbornene of 3 annulus of the total amount of norbornene in 2 annulus or tricyclic member 50 wt _^0/0 or more, more preferably 60 weight _^0/0 It is more preferably at least 70% by weight, most preferably at most 100% by weight. By setting the amount of tricyclic norbornenes to 50% by weight or more of the total amount of bicyclic or tricyclic norbornenes, the properties such as impact resistance and heat resistance of the molded body can be enhanced. Balanced.

 (2) 4 or more ring norbornenes having a specific substituent [C ']

 The third norbornene [C ′] used in the method of the present invention has four or more rings, and is different from the first and second norbornenes [Α ′] and [Β ′]. , That is, at least one substituent having 1 to 4 carbon atoms. Such norbornenes [C '] can be represented by the following formula (C'1).

However, the meaning of each symbol in the above formula (C ′ 1) is the same as in the above formula (C 1).

Examples of the substituent include a hydrocarbon group, a halogen atom, a hydroxyl group, an alkoxycarbyl group, an acyloxy group, an alkoxy group, a cyano group, an amide group, an imido group, a silyl group, and a polar group (a halogen atom, a hydroxyl group, an alkoxy group). And a hydrocarbon group substituted with a carbonyl group, an acyloxy group, an alkoxy group, a cyano group, an amide group, an imido group, or a silyl group). Examples of tetracyclic or more norbornenes having a specific substituent include, for example, tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] —dodeforce-3-ene (tetracyclododecene, And a substituent having at least one substituent having 1 to 4 carbon atoms.

Specifically, for example, 8-methyl tetracyclo ^{[4. 4. 0. 1 2 '5} . I 7' 10] dodeca one 3-E down, 8, 8-dimethyl-tetracyclo [4. 4.0. 1 ² ' ⁵ . ^1-7 · ^{iota upsilon]} de de force one 3-E down, 8 E chill tetracyclo [4.4.1 0.1 ^{2 '5.1 7' 10]} Dodeka 3 E down, 8 _ propyl tetracyclo [ 4.4.1 0.1 ² '. ⁵ 1 ^7' '()] dodecane force one 3-E down, 8- i -. propyltetramethylcyclopentadienyl cyclo [4.4.1 0.1 ^{2' 5} 1 ⁷ - ¹⁰ ] Dode force 3-ene, 8-η-butyltetracyclo [4. 4.0.1 ² ' ⁵ · ¹⁷ · Dode force 3-ene, 8 _ i -butyltetracyclo [4 ^{. 4. 0. 1 2 '5.} I 7' 10] dodecane force one 3-E down, 8- t-butyl tetracyclo ^{[4. 4. 0. 1 2 '5} . 1 7' 1 Π] de de force one 3-E down, 8- (1 '- methylpropyl) tetracyclo ^{[4. 4. 0. 1 2' 5} · I 7 '10] dodeca one 3-E down, 8- (2, single-methylpropyl ) Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dodeca-3-ene, 8-Methyl-1-5- (2'-Methynolecyclohexene 1 4'-yl) Tetracyclo [4 · 4. 0.1 ² ' ^5. I ⁷ ' ¹⁰ ] Dodeca 3 , 8-methylidenetetracyclo [4. 4. 0. 1 ² ' ^5. I ⁷ ' ¹⁰ ] dodeca 3-ene, 8-ethylidenetetracyclo [4. - ₃ _ E down, 8-propylidene tetra cyclo [4 - 4.

0. I ^{2 5} '. I ^{7' 10]} dodecane force one 3-E down, 8- main butoxy tetracyclo [4 - 4. 0.1 ^{2 5} '. ^1-7' '. : De de force one 3-E down, 8-ethoxy tetracyclo ^{[4. 4. 0. 1 2 '.} 5 I 7' 10] Dodeka 3 E down, 8-propoxy tetracyclo [4. 4.0. ^{1 2 '. 5 I 7'} 10] Dodeka 3 _ E down, 8- i - propoxy tetracyclo ^{[4. 4. 0. I 2 '.} 5 1 7' 10] dodecane force one 3-E down, 8 - butoxy tetracyclo ^{[.. 4. 4. 0. I 2} 5 I 7 '10] Dodeka 3 E down, 8- (1' single methylpropoxy) Tet Rashikuro [4.4.1 0.1 ^{2 '3.} I ^{7 '10]} Dodeka 3 E down, 8-t-butoxy-tetracyclo [4.4.1 0.1 ^{2' 5.1 7 '10]} dodecane force one 3-E down, 8- main butoxy carbonylation Rutetorashikuro ^{[4. 4. 0. I 2 '.} 5 I 7' 10] dodecane force one 3-E down, 8 one ethoxycarbonyl - Rutetorashikuro ^{[4. 4. 0. I 2 '.} 5 I 7' 10] dodeca _ 3 - E down, 8-propoxy carbonylation Rutetorashikuro ^{[4. 4. 0. 1 2 '.} 5 1 7' 1 ϋ] Dodeka 3 E down, 8 _ methyl one 8- main butoxy Rubo two Rutetorashikuro ^{[4. 4. 0. I 2 '5} . I 7' 10] dodecane force one 3-E down, 8-methyl-one 8-ethoxycarbonyl-tetracyclo ^{[4. 4. 0. I 2 '5} . I ^{7 '10]} dodecane force one 3-E down, 8- Asechiru O carboxymethyl tetracyclododecene ^{[4. 4. 0. I 2' 5} . I 7 '10] Dodeka 3 E down, 8-flop port Panoiruokishite Torashikuro [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Emissions, 8-arsenide Dorokishi one 9-methylstyrene tetracyclo ^{[4. 4. 0. I 2 '5} . I 7' 10] dodeca one 3-E down, 8- black port one 9-methyl-tetracyclo [4.4 0. 1 ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 1-3, 8-cyanotetracyclo [4. 4. 0. 1 ² ' ⁵ · ¹⁷ ' ^{, 0} ] Dode force 3-E down, 8-methyl-8-Xia Roh tetracyclo ^{[4. 4. 0. 1 2 '5} . I 7' 10] dodecane force one 3-E down, 8-trimethylsilyl tetracyclo [4.4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

Particularly preferred substituents include 8-methyl, 8, ⁸ - dimethyl, 8 Echiru, 8-propyl, 8-i-propyl, 8-n-butyl, 8-i-butyl, 8-t-butyl, 8 — (1'-methylpropyl), 8- (2'-methylpropyl), 8-methyl-5- (2'-methylcyclohexene-1'-yl), 8-methylidene, 8-ethylidene, 8-propylidene Is mentioned.

Other 4 annulus above norbornenes, tetracyclo ^{[6. 5. I 3 '6.} 0 2' 7. 0 9 '13] tetradeca one 4, 10-Zhen, tetracyclo [7. 4. 0. I ³ '. ⁶ 0 ^{2' 7]} tetradec one 4, 1 1-diene, 1, 4-methano - 1, 4, 4 substituents of a, 9 a- Tetorahi mud fluorene; pentacyclo [7. 4. 0. I . ³ '. ⁶ 1 ^{10' 13} 0 ^{2 '7]} pentadeca one 4-E down, pentacyclo [6.5.3 1.1 ^{3' 5} 0 ^{2 '7} 0 ^{9.' 13]} Pentade force -. 4, 10 - Jen, 1 1 Mechiru to Kisashiku port [. 6.6.3 1.1 ^{3 '6-1 10' 13} 0 ^{2 '7-0 9'} '] heptadecyl force one 4-E down, 3 a, 4, 7 , 7a-substituted products such as adducts of tetrahydroindene and cyclopentadiene;

 Among them, it is preferable to use tetracyclic norbornenes, that is, tetracyclododecene derivatives as the third norbornenes [C ′].

Among these tetracyclic or more norbornenes [C '], those having a substituent which is not a polar group are preferable from the viewpoints of improving solution stability after polymerization reaction, chemical resistance of molded article, and low hygroscopicity. ₌

 (3) Content of norbornenes [Α '], []'] and [C] in norbornene monomers

Among norbornene monomers (total amount of monomers), norbornenes (norbornenes having no substituent, norbornenes having four or more rings having a specific substituent) Is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight / ⁰ . That is all. When the content is in such a range, the activity of the ring-opening polymerization reaction is high, which is preferable.

 (4) Other copolymerizable monomer components

 In the norbornene-based monomer, other components other than the non-substituted norbornenes [Α '] and [Β'] and the four- or more-cyclic norbornenes [C '] having a specific substituent are as follows. The monomer component is not particularly limited as long as it is a copolymerizable monomer component. For example, monocyclic cyclic olefin monomers such as cyclobutene, cyclopentene, cyclodexene, cycloheptene, and cyclootatene: 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclodiene Examples thereof include conjugated and non-conjugated cyclic diene monomers such as hebutadiene and 1,3-cyclooctadiene.

 (5) Polymerization catalyst and polymerization method

 Ring-opening polymerization using a metathesis polymerization catalyst using the norbornene-based monomer can be performed according to a known method.

The metathesis polymerization catalyst is not particularly limited, and a known one can be used. Specifically, for example, a catalyst system comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum, a nitrate or an acetylaceton compound, and a reducing agent; titanium, vanadium, zirconium, tandastene And a catalyst system comprising a metal halide or acetyl aceton compound selected from molybdenum and molybdenum; and an organoaluminum compound as a cocatalyst; or JP-A-7-179575, J. Am. Chem. Soc., 1986, 108, 733, J. Am. Chem. Soc., 1993, 115, 9858, and J. Am. Chem. Soc. , 196, 1118, 100 and the like can be used as well-known shrock-type and grapps-type living ring-opening metathesis catalysts. These catalysts are used alone or in combination of two or more. The amount of the catalyst to be used may be appropriately selected depending on the polymerization conditions and the like, but is usually at least (100%), preferably (lZl0000), in a molar ratio to the total amount of norbornene-based monomers. The above is usually less than (lZl0), preferably less than (1Z100). In the present invention, a polymerization activity and selectivity of ring-opening polymerization can be enhanced by further adding a polar compound to the above-mentioned catalyst system. Examples of polar compounds include molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, and molecular compounds. Examples include iodine and other Lewis acids. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethyla-line, tri-n-butylamine, pyridine, α-picoline and the like. These polar compounds may be used alone or in combination of two or more. The amount of the polar compounds used is appropriately selected, but the ratio to the metal in the catalyst, that is, the ratio of the polar compound / metal (molar The ratio is usually 1 or more, preferably 5 or more, and is usually 10000 or less, preferably 10000 or less.

 The polymerization reaction may be performed by bulk polymerization without using a solvent, or may be performed in a solvent such as an organic solvent. The solvent is not particularly limited as long as it is inert to the polymerization reaction. Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; and aliphatic hydrocarbons such as η _ pentane, hexane, and heptane. Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, and bicyclononane; and non-perogenated hydrocarbons such as dichloroethane, chlorobenzene, dichloro / lebenzene, and trichloronobenzene.

The polymerization temperature is usually −50 ° C. or higher, preferably −30 ° C. or higher, more preferably 120 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower And more preferably below 150 ° C. The polymerization pressure is a usually 0 kg Z cm ² or more, usually 5 0 kg / cm ² or less, preferably ² 0 kg / cm 2 or less. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually at least 30 minutes, preferably at least 1 hour, and usually at most 20 hours, preferably at most 10 hours.

 (6) Hydrogenation catalyst and hydrogenation reaction

In the case where the hydrogenated norbornene ring-opening polymer according to the present invention has a repeating unit having an aromatic ring, in the hydrogenation reaction of the carbon-carbon double bond in the main chain structure, Although it is possible to leave the aromatic ring structure of the above, it may be completely hydrogenated. Note that — NMR analysis shows that carbon-carbon double bonds in the main chain structure Can be recognized separately from the unsaturated bond in the aromatic ring structure.

 The hydrogenation is carried out by contacting the ring-opening copolymer with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

 Examples of the hydrogenation catalyst include JP-A-58-433412, JP-A-60-26024, JP-A-64-24826, and JP-A-Hei. The catalysts described in, for example, JP-A-1-1382570 and JP-A-7-415550 can be used, and either a homogeneous catalyst or a heterogeneous catalyst may be used. The homogeneous catalyst is easy to disperse in the hydrogenation reaction solution, so that the amount of addition may be small.In addition, since the catalyst is active even at a high temperature and a high pressure, it does not cause decomposition or gelation of the polymer, resulting in low cost and low cost. Excellent quality stability. Heterogeneous catalysts have high production efficiency at high temperatures and high pressures, can be hydrogenated in a short time, and have excellent production efficiency such as being easily removed.

 As the homogeneous catalyst, for example, a Wilkinson complex, that is, chlorotris (triphenylphosphine) rhodium (I); a catalyst comprising a combination of a transition metal compound and an alkyl metal compound, specifically, cobalt acetate Z triethylaluminum And nickel acetyl acetate sodium triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride Zsec-butyllithium, and tetrabutoxytitanate / dimethylmagnesium.

 Examples of the heterogeneous catalyst include catalysts in which a hydrogenation catalyst metal such as Ni, Pd, Pt, Ru, and Rh is supported on a carrier. In particular, when it is preferable that the amount of impurities and the like is small, it is preferable to use an adsorbent such as alumina-diatomaceous earth as a carrier.

The hydrogenation reaction is usually performed in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the catalyst, but a hydrocarbon-based solvent is usually used because of excellent solubility of the generated hydrogenated product. Examples of the hydrocarbon-based solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicycles such as cyclohexane, methylcyclohexane, decalin, and bicyclonononane. Group hydrocarbons; and among them, cyclic alicyclic hydrocarbons are preferable. Each of these organic solvents is used alone. Alternatively, two or more kinds can be used in combination. Usually, it may be the same as the polymerization reaction solvent, and the reaction may be carried out by adding a hydrogenation catalyst to the polymerization reaction solution as it is. The hydrogenation reaction can be carried out according to a conventional method, but the hydrogenation rate changes depending on the type of the hydrogenation catalyst and the reaction temperature, and the residual rate of the aromatic ring can also be changed. In such a case, control such as lowering the reaction temperature, lowering the hydrogen pressure, or shortening the reaction time may be performed in order to maintain the unsaturated bond of the aromatic ring to a certain extent or more.

In order to selectively increase the hydrogenation rate of unsaturated bonds in the main chain while leaving the aromatic ring structure in the norbornene-based ring-opening copolymer completely without hydrogenation, it is usually necessary to increase the hydrogen pressure. 0. 1 k gZc m ² or more, preferably 0. 5 k gZc m ² or more, more preferably an at 1 k gZc m ² or more, usually 50 k gZc m ² or less, preferably 40 k gZc m ² or less, More preferably, it is 30 kg / cm ² or less. When a homogeneous catalyst is used, the reaction temperature of the hydrogenation reaction is usually at least 10 ° C, preferably at least 0 ° C, more preferably at least 20 ° C, and usually at 150 ° C. The temperature is preferably 130 ° C. or lower, more preferably 110 ° C. or lower. When a heterogeneous catalyst is used, it is usually at least 0 ° C, preferably at least 100 ° C, more preferably at least 150 ° C, and usually at most 300 ° C, preferably at 250 ° C. Below, more preferably, at 230 ° C or lower. Under the condition that the double bond in the main chain structure is hydrogenated, the non-conjugated double bond in the side chain (for example, an alkylidene group) is also hydrogenated.

After the completion of the hydrogenation reaction, the catalyst may be removed according to a conventional method such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added. In applications where it is not desirable for the remaining transition metal to elute, such as medical equipment, it is preferable that substantially no transition metal remains. Use an adsorbent such as alumina having a specific pore volume and specific surface area, such as disclosed in Japanese Patent Publication No. 317411, or wash the resin solution with acidic water and pure water. It is preferable to do so. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. Ro When filtration is carried out, filtration under pressure or filtration under suction may be carried out, and from the viewpoint of efficiency, it is preferable to use a filter aid such as kerosene or perlite.

 Molding material

 The above-mentioned norbornene-based hydrogenated polymer can be used as a molding material as a resin component, and the molding material has transparency, moisture resistance, heat resistance, impact resistance, mechanical strength, solution stability, low Because of its excellent properties such as dielectric constant, low dielectric loss, low water absorption, low moisture permeability, gas barrier property, steam sterilization resistance and chemical resistance, it can be provided as various molding materials. Preferred uses of the molding material include, for example, medical container materials, electric insulating materials, electronic component processing equipment materials, optical materials and the like.

 In addition to the norbornene-based ring-opening polymer hydrogenated product described above, other polymer materials, various additives, and the like can be added to the molding material according to the application field.

 (1) Other polymer materials

 Examples of other polymer materials include rubbery polymers and other thermoplastic resins.

The rubbery polymer is a polymer having a glass transition temperature (T g) of 40 ° C. or lower, and includes a usual rubbery polymer and a thermoplastic elastomer. The viscosity of the rubbery polymer (ML _{1 +4} , 100 ° C.) is appropriately selected according to the purpose of use, and is usually 5 to 200.

Examples of the rubbery polymer include ethylene monoolefin polymer rubber; ethylene monoolefin-polyene copolymer rubber; ethylene such as ethylene methyl methacrylate and ethylene-butyl acrylate; Copolymer with unsaturated carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene vinyl monoacetate; Ethyl acrylate, Butyl acrylate, Hexyl acrylate, 2-Ethylhexyl acrylate, Acryl Polymers of alkyl acrylates such as lauryl acrylate; random copolymers of polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene (meth ) Alkyl acrylate Copolymer, butadiene-1 (meth) alkyl acrylate-acrylonitrile copolymer, butadiene-1 (meth) alkyl acrylate Gen-based rubbers such as lonitrile-styrene copolymer; butylene-isoprene copolymer;

 Examples of the thermoplastic elastomer include aromatic vinyl such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, and hydrogenated styrene-isoprene block copolymer. Examples include a lu-conjugated diene-based block copolymer, a low-crystalline polybutadiene resin, ethylene-propylene elastomer, styrene graft-ethylene-propylene elastomer, a thermoplastic polyester elastomer, and an ethylene ionomer resin. Of these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. No. 6, Japanese Patent Application Laid-Open Nos. Hei 2-3058014, Japanese Patent Application Laid-Open Nos. Hei 3-72512, Hei 7-44909, and the like. be able to.

 These rubbery polymers can be used alone or in combination of two or more. The mixing ratio of the rubbery polymer is appropriately selected according to the purpose of use.

 When the above molding material is used as a medical container material, the transparency of the medical container made of hydrogenated norbornene ring-opening copolymer must not be reduced during heating and pressure treatment such as steam sterilization (steam sterilization). However, by blending a rubbery polymer, whitening during steam sterilization can be effectively prevented. In this case, the mixing ratio of the rubbery polymer is usually at least 0.001 part by weight, preferably at least 0.01 part by weight, based on 100 parts by weight of the hydrogenated norbornene ring-opening copolymer. Part or more, more preferably 0.01 part by weight or more, usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less.

When high impact resistance and flexibility are required, the mixing ratio of the rubbery polymer is usually 0.1 part by weight or less with respect to 100 parts by weight of the hydrogenated norbornene ring-opening copolymer. Above, preferably at least 1 part by weight, more preferably at least 5 parts by weight, usually at most 100 parts by weight, preferably at most 70 parts by weight, more preferably at most 50 parts by weight. Other thermoplastic resins include, for example, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, and polyolefin. Examples include phenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate, norbornene-based ring-opening copolymers other than the present invention, and hydrogenated products thereof.

 These other thermoplastic resins can be used alone or in combination of two or more, and the mixing ratio is appropriately selected within a range not to impair the object of the present invention.

 (2) Various additives

 Additives that are optionally added to the molding material of the present invention can be used without any particular limitation as long as they are generally used in the field of application. Such additives include, for example, stabilizers, lubricants, UV absorbers, crystal nucleating agents, hydrochloric acid absorbers, antistatic agents, dyes, pigments, organic or inorganic fillers, slip agents, anti-fog agents , Natural oils, synthetic oils, waxes, flame retardants, flame retardant aids, compatibilizers, crosslinking agents, crosslinking aids, plasticizers, and the like. For the purpose of adjusting mechanical properties, etc., use different kinds of thermoplastic resins such as polycarbonate, polystyrene, polyphenylene sulfide, polyesterimide, polyester, polyamide, polyarylate, polysulfone, polyethersulfone, etc. Can also be blended.

 Examples of the stabilizer include fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 1,2-hydroxystearate; glycerin monostearate, glycerin distearate, penyu erythritol distearate, penyu erythritol tristearate Polyhydric alcohol fatty acid esters such as stearate; phenol-based antioxidants, phosphorus-based antioxidants, and zeolite-based antioxidants; among them, phenol-based antioxidants are preferred, and alkyl-substituted phenols are preferred. Systemic antioxidants are particularly preferred.

These antioxidants can be used alone or in combination of two or more. The mixing ratio of the antioxidant is usually at least 0.01 part by weight, preferably at least 0.01 part by weight, based on 100 parts by weight of the hydrogenated norbornene ring-opening copolymer. It is at least 5 parts by weight, usually at most 5 parts by weight, preferably at most 1 part by weight.

 As the lubricant, an organic compound such as an ester of an aliphatic alcohol, an ester of a polyhydric alcohol or a partial ester, or inorganic fine particles can be used. Examples of the organic compound include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. No. Examples of the inorganic fine particles include oxides, hydroxides, sulfides, nitrides, and nitrides of Group IA, IIA, IVA, VI, VIIA, VIII, IB, IIB, IIIB, and IVB elements. Chlorides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and their hydrated compounds, and composite compounds centered on them 1 shows natural mineral particles. The average particle size of the inorganic fine particles is not particularly limited, but is preferably from 0.01 m to 3 m.

 These lubricants can be used alone or in combination of two or more. The blending ratio of the lubricant is appropriately selected according to the purpose of use. For example, when the molding material of the present invention is used as a film, the blending ratio is 100 parts by weight of a hydrogenated norbornene-based ring-opening copolymer. On the other hand, it is usually at least 0.001 part by weight, preferably at least 0.05 part by weight, and usually at most 5 parts by weight, preferably at most 3 parts by weight.

 Organic or inorganic fillers include, for example, silica, kieselguhr, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, domite, calcium oxide, calcium carbonate, calcium sulfate, titanium Potassium acid, barium sulfate, calcium sulfite, talc, clay, mai, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron Examples include fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, crosslinked silicone particles, and polystyrene particles.

These fillers may be added alone or in combination of two or more. Can be The mixing ratio of the filler can be appropriately determined according to the function and purpose of use within a range that does not impair the purpose of the present invention.

 There is no particular limitation on the method of adding these other polymer materials and various compounding agents as long as these compounding components are sufficiently dispersed in the hydrogenated norportene ring-opening copolymer. It is carried out by a method of adding at an arbitrary step in the above or adding at an arbitrary step of melt extrusion. When a rubbery polymer is used as a compounding agent, for example, a method in which the resin temperature is kneaded in a molten state using a ribbon blender, a Henschel mixer, a twin-screw kneader, or the like, The solvent is removed by a coagulation method, a casting method, or a direct drying method.

 Molded body

 The molding material can be molded into a sheet, a film, or the like by a known molding method to produce various molded bodies.

 Molding methods include, for example, injection molding, extrusion, extrusion molding, injection blow molding, two-stage blow molding, multilayer blow molding, connection blow molding, stretch blow molding, and rotational molding. Method, vacuum forming method, extrusion forming method, calendar forming method, solution casting method, hot press forming method, inflation method, etc., but the forming method is not limited to a specific forming method as far as possible. As described in Japanese Patent Application Laid-Open No. Hei 4-2766353, gas barrier properties, weather resistance, light resistance, etc. can be further improved by performing multilayer molding with other resins or double-wall molding. It is possible to increase.

 As molded products, transparency, moisture resistance, heat resistance, impact resistance, mechanical strength, solution stability, low dielectric constant, low dielectric loss tangent, low moisture permeability, gas barrier integrity, steam sterilization resistance, chemical resistance, etc. It is useful in a wide range of fields as various molded articles, including medical equipment.

 For example, medical equipment; electrical insulation materials; electronic component processing equipment; optical materials; electronic parts used for light-receiving elements through windows; structural materials and building materials such as windows, equipment parts, and housings; Automotive equipment such as drain cover, tail lamp cover, instrument panel, etc .; speaker connection material, speaker vibration element,

^; Electrical equipment such as containers; for food such as bottles, returnable bottles, and baby bottles Containers; Packaging materials such as wraps; Films, sheets, helmets, and various other applications.

 Medical equipment includes, for example, liquid, powder, or solid drug containers such as bottles, bottle caps, vials, ampoules, prefilled syringes, infusion bags, sealed medicine bags, press-through packages, eye drop containers, and the like; Sampling test tubes for blood tests, blood collection tubes, test cells, sample containers such as sample containers; medical tools such as syringes, syringe rods; sterile containers such as scalpels, forceps, gauze, contact lenses, etc .; beakers 1. Experiments on petri dishes, flasks, test tubes, centrifuge tubes, etc. 'Analytical instruments; medical optical components such as plastic lenses for medical tests; medical fluid infusion tubes, catheters, pipes, fittings, valves, filters, etc. Materials; denture base, denture, artificial heart, artificial root, artificial bone, artificial joints and other artificial organs and parts; But Ru is illustrated. In particular, chemical containers such as prefilled syringes, syringes, etc., have better transparency, heat resistance, chemical resistance, impact resistance, mechanical strength, and steam sterilization resistance than conventional resin products. The property of being excellent is utilized.

 The molded article is excellent in electrical properties such as low dielectric constant and low dielectric loss tangent, and excellent in mechanical strength such as impact resistance and film strength, and is useful in a wide range of fields as an electrical insulating material. For example, general insulating materials such as electric wire and cable coating materials, consumer and industrial electronic equipment, copiers, computers, printers, OA equipment such as TVs and VCRs, and insulating materials for instruments; Film capacitors for electronic equipment, electrical equipment, electric power, medium / low voltage phase advance, etc .; circuit boards such as rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc. High-frequency circuit boards for equipment; base materials for transparent conductive films such as liquid crystal substrates, optical memories, surface heating elements such as automobile and aircraft defrosters; semiconductor encapsulants for transistors, ICs, LSIs, and LEDs; Sealing materials for electric and electronic components such as motors, connectors, switches, and sensors; parabolic antennas, flat antennas, and headers It can be used for structural members.

The above molded body has virtually no impurities eluted from the resin in addition to its physical properties, etc., and is resistant to many chemicals used for processing electronic components, especially to most strong acids except sulfuric acid. Is preferred as an electronic component processing equipment Has properties.

 Equipment for processing electronic components includes: (a) equipment that comes into contact with electronic components such as semiconductors such as ICs and LSIs, hybrid ICs, liquid crystal display elements, and light-emitting diodes; (b) wafers, liquid crystal substrates, and transparent electrode layers Equipment that comes into contact with manufacturing intermediates, such as those with laminated protective layers, protective layers, etc., and (c) in the process of manufacturing electronic components, comes into contact with chemicals used in the processing of manufacturing intermediates or processing liquids such as ultrapure water Refers to equipment.

 (a) Equipment that comes into contact with electronic components and (b) Equipment that comes into contact with intermediates for the production of electronic components include, for example, tanks, trays, carriers, shelters, cases, and other processing and transfer containers; Separation · Protective material such as film;

 (c) Examples of equipment that comes into contact with the processing liquid include pipes such as pipes, tubes, valves, flow meters, filters, and pumps; liquid containers such as sampling vessels, bottles, ampoules, and bags; Can be

 The hydrogenated norbornene-based ring-opening copolymer (composition) of the present invention has excellent transparency, heat resistance, low water absorption, and mechanical toughness. Useful. For example, optical disks, optical fibers, optical cards, optical lenses, optical mirrors, liquid crystal display element substrates, light guide plates, light diffusion plates, polarizing films, retardation films, light diffusion sheets, prism sheets, automotive window materials and roofs Materials, aircraft window materials, vending machine window materials, show window materials, showcase materials, and the like.

 Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and it is needless to say that the present invention can be implemented in various modes without departing from the gist of the present invention. .

 Example

 Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples. However, the present invention is not limited to only these examples. In the following Reference Examples, Examples, and Comparative Examples, parts and% are by weight unless otherwise specified.

In the following Reference Examples, Examples, and Comparative Examples, the methods for measuring various physical properties are as follows. (1) The glass transition temperature was measured by differential operating calorimetry (DSC).

 (2) Unless otherwise specified, the molecular weight is based on cyclohexane as a solvent. It was measured as a polyisoprene conversion value by one-shot chromatography (GPC).

 (3) The hydrogenation rates of the main chain, side chains, and aromatic rings were measured by 'H-NMR.

(4) For the solution stability, a solution adjusted to a concentration of 20% by weight in cyclohexane was stored at 25 ° C, and the solution viscosities immediately after the adjustment and one week later were compared.

(5) The solvent resistance was evaluated based on the critical stress for the evaluation reagent. The 1 4 O kg ί / cm ² or more critical stress The symbol "", and the 1 4 less than 0 kgf Zc m ² as "X". The limiting stress is based on Bergen's 1-to-4 ellipsometry, using fatty acid triglycerides (linoleic acid 50%, oleic acid 25%, palmitic acid 10%, linolenic acid 10%, and stearate 5%) as reagents. A test piece (thickness: 1 mm, 1 cm × 10 cm) immersed in the reagent was attached to a test jig, and measured one hour later based on the position where cracks occurred.

 (6) The impact strength was determined by preparing a test piece (thickness: 3 mm, 5 cm x 5 cm), using a DuPont impact tester (1/8 inch at the tip of the weight cone), and using J'lS—K72 According to 11, the numerical value was shown as 50% breaking energy.

 (7) Tensile strength and tensile elongation were measured according to ASTM-D 638.

 (8) The light transmittance was measured on a test piece having a thickness of 3 mm according to ASTM-D1003.

 (9) The dielectric constant and the dielectric loss tangent were measured at 1 MHz on a test piece having a thickness of 1 mm in accordance with JIS-K6911.

 Example 1

 (Polymerization)

Under a nitrogen atmosphere, tetracyclo ^{[4. 4. 0. I 2 '5} . I 7' 10] dodeca one 3- E emission (T CD) 4. 6 5 parts by weight, tricyclo [4. 3. 0. I ^{2 '5]} de force one 3, 7 - Gen (DCP) 2. 4 5 parts by weight of 8-E chill tetracyclo _{[4. 4. 0. 1 2 5 χ} -.. ι 0 de de force - ₃ - E 3 parts by weight of cyclohexane (ETD) The mixture was dissolved in parts by weight, and 0.3 parts by weight of 1-hexene was added as a molecular weight regulator. To this solution was added a 10 wt% solution of triisobutylaluminum in hexane.

A mixture of 1 part by weight and 0.043 parts by weight of isobutyl alcohol was added. While keeping the solution at 40 ° C, 1.85 parts by weight of TCD4, 22.05 parts by weight of DCP and 27 parts by weight of ETD and 0.6 parts by weight of tungsten hexachloride ⁰ /. 11 parts by weight of hexane solution was added continuously over 2 hours to carry out polymerization.

 0.067 parts by weight of butyldaricidyl ether and isopropyl alcohol were added to the polymerization solution.

The polymerization catalyst was deactivated by adding 0.2 parts by weight of phenol.

 The polymerization conversion was 100%, and the weight ratio of TCDZDCP in the polymer was 65 /

35. The number average molecular weight (Mn) of the polymer measured by GPC (cyclohexane solvent) was 8,000.

 (Hydrogenation)

To 200 parts by weight of the polymerization reaction solution, 2.4 parts by weight of diatomaceous earth-supported nickel catalyst (manufactured by Nissan Gardler; G-96D, nickel loading rate: 58% by weight) and 20 parts by weight of cyclohexane were added. A hydrogenation reaction was performed at 170 ° C and a hydrogen pressure of 45 kgf / cm ² for 2 hours. This solution was filtered with a pressure filter (Leaf Filter-1 manufactured by Ishikawajima-Harima Heavy Industries, Ltd.) using diatomaceous earth as a filter aid to remove the catalyst. 200 parts by weight of the obtained reaction solution containing the polymer hydrogenated product was poured into 400 parts by weight of isopropyl alcohol with stirring to precipitate the hydrogenated product, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, it was dried at 100 ° C. for 24 hours in a vacuum dryer at a reduced pressure of ImmHg or less to obtain 23 parts by weight of a hydrogenated norbornene ring-opening polymer. The remainder of the reaction solution containing the hydrogenated polymer was stored at 25 ° C. under a nitrogen atmosphere.

The number average molecular weight of the obtained hydrogenated product was 16700 (in cyclohexane, in terms of polyisoprene), and the glass transition temperature was 140 ° (: the hydrogenation rate was 99.9% or more. The viscosity of a solution in which 20 parts by weight of cyclohexane was dissolved in 80 parts by weight of cyclohexane was 25, which was 270 cp initially, and 270 cp after storage at 25 ° C. for 4 days, and no change was observed. Similarly, the reaction solution containing the hydrogenated polymer did not show any change in viscosity even after storage at 25 ° C for 4 days. The stability was good.

 To 100 parts by weight of the hydrogenated product was added 0.1 part by weight of tetrakis (methylene-1- (3 ', 5, di-tert-butyl-4'-hydroxyphenylpropionate) methane) as an antioxidant. Using a twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.), melt and knead the mixture at a cylinder temperature of 250 ° C, extrude it into a strand from a die, cut with a pelletizer, and obtain 95 parts of pellets This pellet was molded using an injection molding machine (Robot Shot 100B, manufactured by FANUC) at a resin temperature of 290 ° (:, mold temperature: 100 ° C), and a test piece was formed. Table 1 shows the measurement results of the physical properties of the molded test pieces.

 Example 2

In the same manner as in Example 1, 5.2 parts by weight of TCD, 2.8 parts by weight of DCP and 2 parts by weight of ETD were dissolved in cyclohexane, and 1-hexene and 10 parts of triisobutyl aluminum A mixture of a wt% hexane solution and isobutyl alcohol was added. In the same manner as in Example 1 to the solution, TCD46. 8 parts by weight, DCP 25. 2 0. 6 weight parts and ETD 18 parts by weight of tungsten hexachloride ⁰ /. A cyclohexane solution was added for polymerization. The weight ratio of TCDZDCP in the polymer was 65 to 35. After polymerization, hydrogenation was carried out in the same manner as in Example 1 to obtain 21 parts by weight of a hydrogenated norbornene ring-opening polymer. The remainder of the reaction solution containing the hydrogenated polymer was stored at 25 ° C. under a nitrogen atmosphere, as in Example 1.

The number average molecular weight of the obtained hydrogenated product was 17,800 (in polystyrene in hexahedral hex, in terms of polyisoprene), the glass transition temperature was 140 ° C., and the hydrogenation rate was 99.9% or more. The viscosity of a solution prepared by dissolving 20 parts by weight of the hydrogenated product in 80 parts by weight of cyclohexane has an initial viscosity of 290 cp at 25 ° C and 320 cp after storage at 25 ° C for 4 days. The change was slight. Further, the reaction solution containing the polymer hydride similarly, change in viscosity even after storage for 4 days in 25 ² C is small, the solution weaker qualitative was good.

 The hydrogenated product was mixed with an acid inhibitor in the same manner as in Example 1 and injection-molded to form a test piece. Table 1 shows the measurement results of the physical properties of the molded test pieces.

Example 3 In the same manner as in Example 1, 4 parts by weight of TCD, 4 parts by weight of DCP and 2 parts by weight of ETD were dissolved in cyclohexane, and 1 hexene and 10 wt% of triisobutylaluminum-dimethyl were dissolved. Oral hexane solution: A mixture of the solution and isobutyl alcohol was added. In the same manner as in Example 1 to the solution, TCD 36 parts by weight, DC P 36 parts by Contact and ETD 1 8 0. 6 weight parts and tungsten hexachloride ⁰ /. A cyclohexane solution was added to polymerize. The weight ratio of TCDZDCP in the polymer was 5050. After polymerization, hydrogenation was carried out in the same manner as in Example 1 to obtain 23 parts by weight of a hydrogenated norbornene ring-opening polymer. The remainder of the reaction solution containing the hydrogenated polymer was stored at 25 ° C. under a nitrogen atmosphere in the same manner as in Example 1.

 The number average molecular weight of the obtained hydrogenated product was 16900 (in polyhexene in terms of polyisoprene), the glass transition temperature was 132 ° C., and the hydrogenation rate was 99.9% or more. The viscosity of a solution prepared by dissolving 20 parts by weight of this hydrogenated product in 80 parts by weight of cyclohexane has an initial viscosity of 260 cp at 25 ° C and 260 cp after storage at 25 ° C for 4 days. No change was observed. Similarly, the reaction solution containing the hydrogenated polymer did not show any change in viscosity even after being stored at 25 ° C for 4 days, and the solution stability was good.

 An antioxidant was added to the hydrogenated product in the same manner as in Example 1, and injection molding was performed to form a test piece. Table 1 shows the measurement results of the physical properties of the molded test pieces.

 Comparative Example 1

 In the same manner as in Example 1, 6.5 parts by weight of TCD and 3.5 parts by weight of DCP were dissolved in hexagonal hexane, and 1-hexene and triisobutylaluminum were dissolved.

A mixture of 0 wt% silk mouth hexane solution and isobutyl alcohol was added. In the same manner as in Example 1, 58.5 parts by weight of TCD, 31.5 parts by weight of DCP, and a 0.6% by weight solution of tungsten hexachloride in cyclohexane were added to the solution to carry out polymerization. The weight ratio of TCDZD CP in the polymer was 65 to 35. After polymerization, hydrogenation was carried out in the same manner as in Example 1 to obtain 22 parts by weight of a hydrogenated norbornene ring-opening polymer. The rest of the reaction solution containing the hydrogenated polymer was stored at 25 ° C. under a nitrogen atmosphere in the same manner as in Example 1.

The number average molecular weight of the obtained hydrogenated product is 18200 (in polystyrene The glass transition temperature is 140, in terms of isoprene. C, The hydrogenation rate was 99.9% or more. The viscosity of a solution prepared by dissolving 20 parts by weight of the hydrogenated product in 80 parts by weight of cyclohexane had an initial viscosity of 70 cp at 25 ° C, but was stored at 25 ° C for 4 days. After that, it had no fluidity and had solidified. Similarly, the reaction solution containing the hydrogenated polymer was solidified after storage at 25 ° C for 4 days, and the stability of the solution was poor.

 An antioxidant was added to the hydrogenated product in the same manner as in Example 1, and injection molding was performed to form a test piece. Table 1 shows the measurement results of the physical properties of the molded test pieces.

 Comparative Example 2

 In the same manner as in Example 1, 5 parts by weight of TCD and 5 parts by weight of DCP were dissolved in a hexahedral hexane, and a solution of 1-hexene and triisobutylaluminum in a 10 wt% silk hexane solution was obtained. And a mixture of isobutyl alcohol was added. In the same manner as in Example 1, 45 parts by weight of TCD, 45 parts by weight of DCP, and a 0.6% by weight cyclohexane solution of tandastene hexachloride were added to this solution, and polymerization was performed. The weight ratio of TCD / DCP in the polymer was 50 / 50.After polymerization, hydrogenation was carried out in the same manner as in Example 1 to obtain 23 parts by weight of a hydrogenated norbornene ring-opening polymer. Was. The remainder of the reaction solution containing the hydrogenated polymer was stored at 25 ° C. under a nitrogen atmosphere in the same manner as in Example 1.

 The obtained hydrogenated product had a number average molecular weight of 1870 (in polystyrene hexane, in terms of polyisoprene), a glass transition temperature of 130 ° C, and a hydrogenation rate of 99.9% or more. The viscosity of a solution prepared by dissolving 20 parts by weight of this hydrogenated product in 80 parts by weight of cyclohexane had an initial viscosity of 38 cp at 25 ° C., but was kept at 25 ° C. for 4 days. After storage, it had no fluidity and had solidified. Similarly, the reaction solution containing the hydrogenated polymer was solidified after storage at 25 ° C for 4 days, and the stability of the solution was poor.

An antioxidant was added to the hydrogenated product in the same manner as in Example 1, and injection molding was performed to form a test piece. Table 1 shows the measurement results of the physical properties of the molded test pieces. 1

(TCD / D

 Weight of three components Impact resistance Tension

 Polymer group light transmission

 CP) Weight Tg

 n Solution Melting resistance Tensile strength

 Composition ratio (.c) Stability D Agent Strength Elongation Permittivity Dielectric loss tangent ratio (I) (%)

 TCD / DCP /

Example 1 46.5 / 24.5 / 30 65/35 16,700 140

 ETD good 〇> 10 640 30 92 2.35 0.0005

TCD / DCP /

Example 2 52/28/20 65/35 17,800 HO

 ETD ft 〇 10> 10 640 30 92 2.35 0.0005

TCD / DCP /

Example 3 40/40/20 50/50 16,900 132

 ETD good o> 10 630 45 92 2.35 0.0005 Comparative Example 1 TCD / DCP 65/35 18,200 140 Poor 〇> 10 635 45 92 2.35 0.0005 Comparative Example 2 TCD / DCP 50/50 18,700 130 Poor 〇> 10 620 80 92 2.35 0.0005

Claims

Scope of word blue 1. Repeating units [A] and [B] derived from at least two unsubstituted norbornenes and at least one substituent having at least 1 and no more than 4 carbon atoms And a repeating unit [C] derived from four or more norbornenes. 2. The repeating unit [A] is a repeating unit derived from a tetracyclic or more norbornene having no substituent or force, and the repeating unit [B] has no substituent. 2. The norbornene-based ring-opening copolymer according to claim 1, which is a repeating unit derived from a cyclic or tricyclic norbornene. 3. The repeating unit [A], the following formula (A1)

A repeating unit represented by the formula: wherein the repeating unit [B] is the following formula (B 1)

Or the following formula (B 2)

2. The norbornene-based ring-opening system according to claim 1, wherein a and b in the above formula are 0, 1 or 2, and 丄 ··· is a carbon-carbon single bond or a double bond. Polymer. 4. The repeating unit according to claim 1, wherein the repeating unit [C] is a repeating unit derived from a tetracyclic or more norbornene having an alkyl group or an alkylidene group having 1 to 4 carbon atoms. Norbornene ring-opening copolymer. 5. Among the repeating units [A], [B] and [C], the repeating units [A] and [B] are 30% by weight or more and 80% by weight or less, and the repeating unit [C] is 20% by weight or more and 70% by weight. 2. The norbornene-based ring-opening copolymer according to claim 1, wherein the content of the repeating unit [A] is 5% by weight or more and 95% by weight or less among the repeating units [A] and [B]. 6. The norbornene ring-opening copolymer according to claim 1, wherein the proportion of the repeating unit having a carbon-carbon double bond in the main chain structure is 20 mol% or less. 7. At least two unsubstituted norbornenes [Α '] and [Β'], and at least four substituents having at least one substituent having 1 to 4 carbon atoms A ring-opening polymerization of a norbornene-based monomer containing norbornene [C '] in the presence of a metathesis polymerization catalyst, Hydrogenating at least 80% of carbon-carbon double bonds in the main chain structure of the obtained ring-opened polymer. 8. The norbornene [Α '] is a 4- or more-ring norbornene having no substituent, and the norbornene [Β'] is a 2- or 3-cyclic norbornene having no substituent. 8. The method for producing a norbornene-based ring-opening copolymer according to claim 7, wherein 9. The norbornenes [Α '] represented by the following formula (Α'1)

A norbornene represented by the formula: wherein the norbornene [Β '] force The following formula (Β'1)

Or the following formula (Β '3)

8. The norbornene-based ring-opening system according to claim 7, wherein a and b in the above formula are 0, 1 or 2, and ··· ′ is a carbon-carbon single bond or a double bond. A method for producing a polymer. 10. The norbornene-based ring-opening copolymer according to claim 7, wherein the norbornene [C '] is a tetracyclic or more norbornene having an alkyl group or alkylidene group having 1 to 4 carbon atoms. Manufacturing method. 1 1. The norbornene [Α '], [Β' ] and [C '] among the norbornenes [Alpha'] and [beta '] is 80 wt _^0/0 to 30 wt% or more, nor bornene acids [ C '] is 20% by weight or more and 70% by weight or less, norbornenes Of [Α '] and [Β'], norbornenes [Α '] are 5% by weight or more 95% by weight ⁰ /. 8. The method for producing a norbornene-based ring-opening copolymer according to claim 7, wherein 1 2. The norbornene ring-opening copolymer according to claim 1, having a glass transition temperature of not less than 20 ° C and not more than 250 ° C. 1 3. The norbornene ring-opening copolymer according to claim 1, having a number average molecular weight of 5,000 to 500,000. 14. The norbornene-based ring-opening copolymer according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight is 5 or less. 1 5. A molding material containing the norbornene-based ring-opening copolymer according to claim 1. 16. The molding material according to claim 15, further comprising a rubbery polymer. 17. The molding material according to claim 15, further comprising a stabilizer. 18. The molding material according to claim 15, further comprising a lubricant or a filler. 19. A molded article obtained by molding the molding material according to claim 15.