WO1994002521A1 - Hydrogenated resin - Google Patents

Abstract

A hydrogenated resin which is produced by hydrogenating a polymer containing repeating units of linear poly-addition type comprising cyclopentadiene monomer, wherein at least 90 % of the carbon-carbon double bonds in the repeating units are hydrogenated, and which has the limiting viscosity of 0.1-10 dl/g as measured in toluene at 25 °C. This resin does not contain cross-linked gel, is excellent in clarity, lightfastness, moisture resistance, moldability, mechanical strengths and chemical resistance, and has a low birefringence, thus being suitable as optical materials, medical polymer materials, electrical insulation materials, electronic component materials, and so forth.

Description

 Description Hydrogenated resin Technical field

 The present invention relates to a hydrogenated resin, and more particularly, to a resin obtained by hydrogenating a polymer containing a linear addition polymerization type repeating unit of a cyclopentadiene monomer. The hydrogenated resin of the present invention is excellent in transparency, light resistance, moisture resistance, low dielectric constant, low dielectric loss, chemical resistance, etc., and is particularly suitable for optical materials, medical polymer materials, electrical insulating materials, and electronic components. It is suitable as a material. Background art

 Hitherto, polymethyl methacrylate-polycarbonate has been used as an optical polymer material, but the former has problems such as large water absorption and the latter has large birefringence of injection molded products. As a result, it is becoming increasingly difficult to respond to the demand for increasingly sophisticated optical polymer materials.

 Polymer materials that have improved these disadvantages include, for example, hydrogenated ring-opening polymers of norbornene-based monomers and thermoplastic saturated polymers such as addition-type copolymers of norbornene-based monomers and ethylene. The fact that the norbornene-based polymer has excellent characteristics as an optical disc substrate material has been disclosed in Japanese Patent Application Laid-Open Nos. Sho 60-26024, Sho 62-24826, Sho 62 This is disclosed in, for example, Japanese Patent Application Laid-Open No. 0-1688708, Japanese Patent Application Laid-Open No. S61-115912, and Japanese Patent Application Laid-Open No. 61-12816.

However, in these prior arts, in general, norbornene-based Polycyclic monomers such as tetracyclododecenes are used as monomers, but production of polycyclic monomers is not always easy. Normally, polycyclic monomers are synthesized by an addition reaction of norbornenes and dicyclopentene (hereinafter, referred to as DCP) under heating, but are synthesized by the addition of cyclopentene (hereinafter, referred to as CPD) multimers. Since it contains many products, it is necessary to purify and separate it by distillation and the like, and it is difficult to purify and separate it. Therefore, polycyclic monomers, especially tetracyclododecene derivatives, are very expensive and not industrially advantageous. Also, the types of monomers available are limited. In contrast, bicyclic norbornene-based monomers are easily available at low cost, but their ring-opened polymers have too low a glass transition temperature (T g) and have poor heat resistance. The addition-type polymer had a Tg of 300 ° C. or higher and was inferior in moldability and could not be used for general purposes.

- How, CPD is easily available as a C ₅ fraction in the petrochemical industry, usually by a pressurized heat decomposes this what is stored as a DCP or more 1 8 0 ° C, obtained in high purity Can be CPD is used as a tackifier by obtaining a linear addition polymer by a method such as cation polymerization (Ann., 447, 1110, 1926) Ind. En. Chem., 18, 38 1, 19 26; Polymer Chemistry, i_, 73, 1962; Polymer Chemistry, 56, 196 6; Japanese Unexamined Patent Publication No. 55-65220). However, since the linear addition polymer of CPD contains many unsaturated bonds, it is extremely susceptible to air oxidation, its strength is deteriorated, it is difficult to melt, and its moldability is deteriorated.

When a large amount of an antioxidant is added to the CPD linear addition polymer to prevent oxidation, color tone deterioration is improved, but there are problems such as bleeding of the antioxidant. Can be used as a material There was no. It is also known that this polymer is partially hydrogenated to improve its oxidation resistance (Polymer Chemistry, 734, 1962). It is not easy to hydrogenate the coalescence, and even those with a low molecular weight of intrinsic viscosity [7?] Of about 0.06 d 1 g are known to have a hydrogenation rate of about 73%. Thus, for example, a polymer having excellent stability required for optical materials and the like has not been known.

 Recently, a method for obtaining a relatively high-molecular cycloolefin polymer using a polymerization catalyst comprising a transition metal compound and an aluminoxane has been developed (Japanese Unexamined Patent Publication No. 3-254048). This document also discloses that addition polymerization of a norpolene-based monomer and cycloolefin is carried out.Examples showing such specific examples, particularly examples using CPD as the orefin, are not described. It was not disclosed, and it was not known that addition copolymerization of a norbornene-based monomer and CPD was performed and what properties of a hydrogenated product of the copolymer had.

 Furthermore, addition polymers having a cycloalkane structure in the side chain, such as polyvinylcyclohexane, polystyrene, polyvinylcyclohexene, and polyvinylcyclopentene, are excellent in terms of low birefringence, heat resistance, and low moisture absorption. It has been known that it can be used as an optical material (JP-A-63-43910, JP-A-1-132603, etc.). However, these polymers have insufficient mechanical strength, so there is a problem in using them as general optical materials, and other specific uses have not been sufficiently studied. Disclosure of the invention

The objectives of the present invention are: 'transparency, light resistance, moisture resistance, low dielectric constant, low dielectric loss An object of the present invention is to provide a resin material which is excellent in loss, chemical resistance, and the like, and is particularly suitable as an optical material, a medical polymer material, an electrical insulating material, an electronic component material and the like.

 As a result of intensive studies, the present inventors have succeeded in developing a resin obtained by hydrogenating a polymer containing a linear addition polymerization type repeating unit of a cyclopentadiene monomer. This hydrogenated resin is a linear addition-polymerized homopolymer of a cyclopentagen-based monomer or a linear addition-polymerized copolymer of a cyclopentagen-based monomer and a vinyl group-containing cyclic hydrocarbon monomer. It is a resin obtained by hydrogenating a linear addition-polymerized copolymer of cyclopentadiene-based monomer and norbornene-based monomer, etc., does not contain cross-linked gel, and has transparency, low birefringence, It has excellent light resistance, moisture resistance, moldability, mechanical strength, chemical resistance, etc., and is suitable as an optical material, medical polymer material, electrical insulating material, electronic component material, and the like. The present invention has been completed based on these findings.

 Thus, according to the present invention, there is provided a resin obtained by hydrogenating a polymer containing a linear addition polymerization type repeating unit of a cyclopentadiene monomer, wherein the carbon-carbon double At least 90% of the bonds are hydrogenated and a hydrogenated resin with an intrinsic viscosity measured in toluene at 25 [7?] Force 0.1 to 10 d 1 / g is provided. . The polymer is not limited to a homopolymer of a cyclopentadiene monomer, but may be a copolymer of a cyclopentadiene monomer and a monomer copolymerizable with the monomer. Good.

As the copolymer, in particular, 10 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and a linear addition polymerization of a vinyl group-containing cyclic hydrocarbon monomer Mold repeating unit 90 ~ 50 weight % Of a linear addition polymerization type repeating unit of a cyclopentene-based monomer and a linear addition polymerization type repeating unit of a norbornene-based monomer. Copolymers containing 0 to 50% by weight are preferred, and as the hydrogenated resin, at least 90% of carbon-carbon double bonds in these copolymers are hydrogenated. The ones you like are preferred.

 Hereinafter, the present invention will be described in detail.

 (Monomer)

Cyclopentadiene monomer

 The cyclopentadiene monomer used in the present invention is CPD or an alkyl-substituted product thereof. Specific examples thereof include CPD, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene and 5,5-dimethylcyclopentene. These can be used alone or in combination of two or more. Copolymerizable monomers

 The cyclopentadiene-based monomer can be used in combination with a monomer copolymerizable with the cyclopentadiene-based monomer.

Monomers copolymerizable with cyclopentene-based monomers include ethylene, propylene, isobutene, dipentene, limonene, vinylcyclohexene, 2-methyl-1-butene, and 2-methyl-1-butene. Α-olefins such as butene, isoprene, 1,3-pentadiene, furan, thiophene, etc .; ethylene oxide, propylene oxide, trimethylene oxide , Trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin, tetrahydro Cyclic ethers such as drofuran: vinyl ethers such as methyl vinyl ether and ethylvinyl ether; vinyl compounds containing heterocycles such as vinyl pyridine, N-vinyl carbazole, N-vinyl-2-pyrrolidone; cyclopentene, cyclohexene , Norbornadiene, 1,3-cyclohexadiene, and substituted products thereof, such as cyclic olefins; vinyl group-containing cyclic hydrocarbon monomers; norbornene monomers; and the like.

 These copolymerizable monomers are used within the range where the properties such as the heat resistance, flexibility, moldability, mechanical strength, etc. of the target hydrogenated resin are not substantially impaired, or these properties are improved. In order to improve them, they can be used singly or in combination of two or more kinds in a desired copolymerization ratio. Specifically, the copolymerization ratio should be selected within the range of 10 to 100% by weight of cyclopentagen-based monomer and 90 to 0% by weight of these copolymerizable monomers. Can be. Generally, when the proportion of the copolymerizable monomer other than the vinyl group-containing cyclic hydrocarbon monomer and the norbornene monomer is increased, the resulting hydrogenated resin becomes transparent, colorless, and low in complexity. Refractive properties etc. decrease. Therefore, when α-olefin, conjugated diene, cyclic ether, vinyl ether, heterocyclic vinyl compound, or cyclic olefin is used as the copolymerizable monomer, The monomer is generally used in a proportion of not more than 40% by weight, preferably not more than 25% by weight, more preferably not more than 10% by weight.

On the other hand, vinyl group-containing cyclic hydrocarbon-based monomers or norbornene-based monomers improve the Tg of the copolymer, and provide transparency, low birefringence, light resistance, moisture resistance, moldability, and mechanical properties. Used in a wide range to improve the heat resistance of hydrogenated resins without impairing mechanical strength, chemical resistance, etc. Can be Specifically, 10 to 90% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and a linear addition polymerization of a vinyl group-containing cyclic hydrocarbon monomer or a norbornene monomer. Copolymers containing 90 to 10% by weight of repeating units of the type can be used. In particular, 10 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and a linear addition polymerization type repeating unit of a vinyl group-containing cyclic hydrocarbon monomer or a norbornene monomer. Copolymers containing 90 to 50% by weight of a unit are preferred because they can provide a hydrogenated resin having an excellent balance of heat resistance and other physical properties. In order to produce a copolymer containing such a repeating unit, since the reactivity of each monomer is different, the monomer composition to be used is determined according to the reactivity of each monomer. In general, the cyclopentadiene monomer has high reactivity, so that the cyclopentadiene monomer is usually 5 to 90% by weight and the vinyl group-containing cyclic hydrocarbon monomer or the norbornene monomer 9 It is used in the range of 5 to 10% by weight.

Therefore, in applications where heat resistance is required, the vinyl group-containing cyclic hydrocarbon-based monomer or norbornene-based monomer is usually at least 10% by weight, preferably at least 20% by weight, more preferably at least 3% by weight. Use 0% by weight or more. In particular, in applications where heat resistance is required, 50 to 95% by weight of these monomers, preferably 55 to 90% by weight, more preferably 60 to 80% by weight, The content of the cyclopentadiene monomer can be 5 to 50% by weight, preferably 10 to 45% by weight, and more preferably 20 to 40% by weight. In this case, other copolymerizable monomers such as α-olefin, conjugated gen, cyclic ether, vinyl ether, heterocycle-containing vinyl compound or cyclic olefin are combined with 40% of the entire monomer composition. Wt% or less, preferably 25 wt% or less, more preferably Alternatively, it may be used in a proportion of 10% by weight or less.

Vinyl group-containing cyclic hydrocarbon monomer

 Examples of the vinyl group-containing cyclic hydrogen monomer used in the present invention include vinyl cyclopentene monomers such as 4-vinylcyclopentene, 2-methyl-1-isopropenylcyclopentene, 4-vinylcyclopentane, and 4-vinylcyclopentane. Vinyl-containing 5-membered hydrocarbon monomers such as pentane-based monomers such as pentane-based monomers such as isopropenylcyclopentane; 4-vinylcyclohexene, 4-vinylpropene-hexene,

1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methisolate 4-beninolecyclohexene,

2-cyclohexene monomer such as 2-cyclohexene, 2-vinylcyclohexene, 2-cyclohexene such as 2-methylcyclohexene, etc. Hexane monomer, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-styrene monomer such as 4-phenylstyrene, d-terpene, 1 6-membered ring hydrocarbon monomer containing vinyl group such as terpene monomer such as mono-terpene and diterpene; vinyl cycloheptene such as 4-vinylcycloheptene and 4-isopropenylcycloheptene 7-membered ring containing vinyl group such as vinylcycloheptane monomer such as 4-monomer, 4-vinylcycloheptane, 4-isopropenylcycloheptane Examples include hydrocarbon monomers.

 These monomers can be used alone or in combination of two or more. Among them, a vinyl group-containing six-membered ring hydrocarbon-based monomer is preferred.

Norbornene monomer Examples of the norbornene-based monomer used in the present invention include norbornene and derivatives thereof. For example, 2-norbornene, 5-methyl-2-nonorebornene, 5,5-dimethyl-1-nonorebornene, and 5-ethyl- 2-norbornene, 5-butylnorbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-methoxycarbonyl 2-norenobornene, 5-cyano-2-norbornene, 5-methyl-5 —Methoxycarbonol 2 —Norbornene, 5—Fenil 2—Norbornene, 5—Fenil 5—Methyl-1-Norbornene, 5—Hexyl 2-Nonorebornene, 5-Octyl-2—Nonorebornane, Norbornene, such as 5-octadecyl-2-norbornene, its alkyl, alkylidene, and alkenyl Or an aromatic substituted derivative, a polar group substituent such as a halogen, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imido group or a silyl group; 1, 4: 5,8- Dimethano 1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methyl-1,4: 5,8-dimethano 1,4,4a, 5,6, 7, 8, 8a—Octahydronaphthalene, 6—Ethyl-1,4: 5,8—Dimetano-1,4,4a, 5,6,7,8,8a—Octahydronaphthalene, 6 —Ethylidene 1,4: 5,8—Dimethano 1,4,4a, 5,6,7,8,8a—Octahydronaphthalene, 6—Methyl-6—Methoxycarbonyl-1, 4: 5,8—Dimetano-1,4,4a, 5,6,7,8,8a—Octahydronaphthalene, 6—Syano-1,4: 5,8—Dimetano-1,4 , 4 a, 5, 6, 7, 8, 8 a Monomers in which one or more CPDs are added to norbornene, such as dronaphthalene, and derivatives or substitutes thereof as described above; DCP, 1,4: 5,8-dimethano-1,2,3, 4, 4 a, 5, 8, 8 a-2, 3 — Clopentadienonaphthaletalene, 1,4: 5,10: 6,9 — Trimethano-1,2,3,4,4a, 5,5a, 6,9,9a, 10,10 a-dodecahydro-2,3-cyclopentadienoanthracene, 2,3-dihydroxycyclopentadiene, etc., a monomer having a polycyclic structure which is a multimer of CPD, and derivatives or substitutes similar to the above. 1,4-metano-1,4,4a, 4b, 5,8,8a, 9a—octahydrofluorene, 5,8—methano1,2,3,4 Adducts of CPD, such as 1,2,3-cyclopentadienonaphthalene, etc. with 4,4-, 5,8,8a-octahydro-1,2-cyclopentadienonaphthalene, and derivatives and substituents similar to those described above; No.

 These monomers can be used alone or in combination of two or more. Of these, bicyclic monomers are preferred from the standpoint of availability. In addition, from the viewpoint of improving heat resistance, these monomers are preferred as having a large number of rings, but if the heat resistance is excessively improved, it becomes difficult to perform melt molding. In such cases, a bicyclic compound is preferred.

 (Polymerization catalyst)

 In the present invention, the polymerization catalyst used for the polymerization of the monomer composition of the cross-opening pentadiene-based monomer or the cross-opening pen-nitrogen-based monomer and a monomer copolymerizable therewith is a linear addition ( The copolymer is not particularly limited as long as it can be polymerized, and known cationic polymerization catalysts, living cation polymerization catalysts, Ziegler catalysts and the like can be used.

As the cationic polymerization _{catalyst, A 1 C 1 3, A} 1 B r 3, BF 3, BC 1 3, BF 3 * OE ", T i C l" T i B r 4, Fe C l 3, F e C _{l 2, SnC ", S n} C l 4, T i C l 4 / C l 3 CCOOH, a metal halide such _{S n C 1 4 / C l} 3 C COOH, WC 1 6, M o C 1 5; P d (CH ₃ CN) ₂ C 1 ₂ 4025 1

 11

_{, P d (C 6 H 5} CN) 2 C 1 2, P d (CH 3 CN) 4 (BF 4) P d catalysts such as _{2; HC 1, HF, HB} r, H 2 S 0 4, H 3 B 0 ₃ , HC 1 0 ₄

_{, CH 3 CO OH, C 1} 3 CC 00 H hydrogen acid and the like; and the like, in a re-interleaving the cationic polymerization catalyst used in combination with a Lewis acid initiator compound, T i C l ₄ Z2- main Tokishi 2—Phenylpropane, T i Cl ₄

Z _{t-butanol, T i C l 4 Z l} , 4 - bis (2-main butoxy one 2 one propyl) benzene, 2- Fuweniru 2-propanol, etc. are elevation Gerare, as the Ziegler catalyst, T i C l ₄ such as a single E t ₃ A l can be mentioned.

 The amount of the polymerization catalyst used is usually in the range of 0.000001 to 1 times, preferably 0.00001 to 0.5 times, in molar ratio, relative to the monomer component.

 (Polymerization reaction solvent)

 The polymerization is usually carried out using a solvent. Examples of the solvent include aromatic solvents such as benzene, toluene and xylene; hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, and decalin; Halogenated hydrocarbons such as methyl, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2—trichloroethylene And hydrocarbon solvents, particularly cyclopentane, cyclohexane, methylcyclohexane, and decalin, are preferred because of their excellent solubility of the polymer.

 (Polymerization temperature)

The polymerization temperature is usually in the range from −150 to 100 ° C., preferably from −100 to 50 ° C., particularly preferably from 150 to 50 ° C. If the temperature is too high, it reacts violently, making it difficult to control the reaction and causing gelation. Or thermal deterioration. Also, if the temperature is too low, the reaction speed is slow and inefficient.

 (Polymer)

 The polymer of a cyclopentene monomer used in the present invention is a polymer containing a linear addition polymerization type repeating unit represented by the following general formula (I) and / or (π). .

(In the formula, R ^{1 to} R ⁶ each represent a hydrogen atom or an alkyl group.)

(In the formulas, R ^{7 to} R ¹² each represent a hydrogen atom or an alkyl group.) In the general formulas (I) and (と し て), the alkyl group includes a carbon atom having 1 carbon atom such as a methyl group or an ethyl group. About 5 lower alkyl groups are preferred.

A polymer containing a linear addition polymerization type repeating unit of a cyclopentadiene monomer has an intrinsic viscosity [7?] Measured in toluene at 25 ° C of 0.1 to 10 dl / g, Preferably it is of 0.2 to 5 dl Z g, more preferably of 0.3 to 2 dl / g. If the intrinsic viscosity is too low, the mechanical strength of a molded product of a hydrogenated product of the polymer becomes low, If the limiting viscosity is too large, it becomes difficult for the hydrogenation reaction of the polymer to proceed smoothly. Further, since the polymer used in the present invention does not substantially contain a gel, it is soluble in a suitable solvent and can smoothly carry out a hydrogenation reaction.

 A sο, C., et al., J. Pol ym er Sci.,

Calculated based on the Aso method described in Part B 4,701 (1966), it contains a linear addition-polymerized repeating unit of the cyclopentadiene monomer used in the present invention. In the polymer, the repeating unit represented by the general formula (I) is usually 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. is there. The proportion of the repeating unit represented by the general formula (I) is determined by the polymerization catalyst, the polymerization solvent, and the like, and is substantially unaffected by the presence of the comonomer and the polymerization temperature.

 When a cyclic pentadiene monomer and a vinyl group-containing cyclic hydrocarbon monomer are copolymerized, a repeating unit represented by the above general formula (I) and Z or (Π), A copolymer containing a repeating unit derived from a hydrocarbon monomer is obtained. When the vinyl group-containing cyclic hydrocarbon monomer is a five-membered ring, a six-membered ring or a seven-membered ring, a repeating unit represented by the following general formula (m), (W) or (V), respectively. Unit.

(ΠΙ)

(In the formula, R ^{13 to} R ²⁴ each represent a hydrogen atom or an alkyl group, and among them, R ^{16 to} R ²⁴ represent carbon atoms adjacent to each other and may form a double bond.)

(In the formula, R ² R ³⁸ represents a hydrogen atom or an alkyl group, wherein R ^: 'R ³⁸ represents carbon atoms adjacent to each other and may form a double bond.)

(Wherein, R ^{39 to} R ⁵ each represent a hydrogen atom or an alkyl group, and among them, R ^{42 to} R ⁵⁴ represent carbon atoms adjacent to each other and may form a double bond.)

 In these general formulas (HI), (IV) and (V), the alkyl group is preferably a lower alkyl group having about 1 to 5 carbon atoms, such as a methyl group or an ethyl group.

These repeating units represented by the general formulas (m), (IV) and (V) may be used alone or in combination of two or more. Is also good.

 In the copolymer, the linear addition polymerization type repeating unit of the vinyl group-containing cyclic hydrocarbon monomer is usually in the range of 10 to 90% by weight. In particular, when heat resistance is required, the linear addition polymerization type repeating unit of the vinyl group-containing cyclic hydrocarbon monomer is usually 50 to 90% by weight, preferably 55 to 80% by weight. % By weight, more preferably 60 to 70% by weight. The remainder is a repeating unit represented by the general formula (I) and Z or (ま た は). However, if desired, a repeating unit derived from other copolymerizable monomers such as one-year-old refine, conjugated gen, cyclic ether, vinyl ether, heterocyclic vinyl compound or cyclic olefin may be used as a minor component. May be contained. Also 25 of this copolymer. The intrinsic viscosity [7?] Measured in toluene of C is 0.1 to 10 d1 Zg, preferably 0.2 to 5 dl / g, more preferably 0.3 to 2 dl / g. .

 If the linear addition polymerization type repeating unit of the vinyl group-containing hydrocarbon monomer is too large, the melting temperature becomes too high, so that melt molding becomes difficult or the mechanical strength decreases. If there are too many linear addition polymer-type repeating units of the cyclopentadiene monomer, heat resistance will be reduced.

The polymer of a cyclopentadiene monomer and a vinyl group-containing cyclic hydrocarbon monomer is a novel polymer, and in particular, is a linear addition-polymerized repeating unit of a cyclopentadiene monomer 10 to 50 A copolymer containing 50% by weight and 50 to 90% by weight of a linear addition polymerization type repeating unit of a vinyl group-containing cyclic hydrocarbon monomer has transparency and low birefringence without hydrogenation. Excellent in heat resistance, light resistance, moisture resistance, moldability, mechanical strength, chemical resistance, etc., and can be used as optical materials, medical polymer materials, electrical insulating materials, electronic component materials, etc. . However, light resistance deterioration The hydrogenated product of the copolymer is superior in terms of properties, heat deterioration resistance, chemical resistance and the like.

 When the cyclopentadiene-based monomer and the norbornene-based monomer are copolymerized, the repeating unit represented by the general formula (I) and / or (Π) and the norbornene-based monomer A copolymer having a repeating unit derived therefrom is obtained.

 Examples of the repeating unit derived from the norbornene monomer include a linear addition polymerization type repeating unit represented by the following general formula (VI).

(In the formula, n is 0, 1 or 2, and R ^{55 to} R ⁶⁶ each represent a hydrogen atom, an alkyl group, an alkylidene group, an alkenyl group, an aromatic substituent or a polar substituent.)

 Here, as the alkyl group, alkylidene group, alkenyl group, aromatic substituent and polar substituent in the general formula (VI), those shown in the examples of the monomer can be exemplified.

In the copolymer, the repeating unit of the linear addition polymerization type of the norbornene-based monomer is usually in the range of 10 to 90% by weight. When heat resistance is particularly required, the repeating unit of the linear addition polymerization type of norbornene-based monomer is usually 50 to 90% by weight, preferably 55 to 80% by weight, More preferably, it is 60 to 70% by weight. The remainder is a repeating unit represented by the general formula (I) and / or (Π). However, if necessary, repeating units derived from other copolymerizable monomers such as α-olefins, conjugated gens, cyclic ethers, vinyl ethers, heterocyclic-containing vinyl compounds or cyclic olefins may be used as minor components. May be included. In addition, the intrinsic viscosity ["] of this copolymer measured in toluene at 25 ° C is from 0.1 to 10 dl Zg, preferably from 0.2 to 5 dl / g, more preferably from 0.2 to 5 dl / g. Is 0.3-2 dl / g.

 If the linear addition polymerization type repeating unit of norbornene-based monomer is too large, the melting temperature becomes too high, so that melt molding becomes difficult or mechanical strength decreases. If there are too many linear addition polymerization type repeating units of the cyclopentadiene monomer, heat resistance will be reduced.

 The polymer of a cyclopentadiene-based monomer and a norbornene-based monomer is a novel polymer. In particular, a linear addition-polymerized repeating unit of a cyclopentadiene-based monomer is 10 to 50% by weight. A copolymer containing 50 to 90% by weight of a norbornene-based monomeric linear addition polymerization type repeating unit can have transparency, low birefringence, light resistance, and moisture resistance without hydrogenation. It excels in properties, moldability, mechanical strength, and chemical resistance, and can be used as optical materials, medical polymer materials, electrical insulating materials, electronic component materials, and so on. However, the hydrogenated product of the copolymer is superior in terms of light deterioration resistance, heat deterioration resistance, chemical resistance and the like.

(Hydrogenation)

Hydrogenation catalyst

The hydrogenation catalyst can be used as long as it is generally used in hydrogenation of an orifice compound, for example, Wilkinson complex, cobalt acetate Z triethylaluminum, nickel acetyl Heterogeneous catalysts in which catalytic metals such as Nigel, Palladium, and Platinum are supported on acetonate Z triisobutylaluminum, diatomaceous earth, magnesium, alumina, synthetic zeolite, etc. among ', magnesia, active alumina, synthetic Zeorai pores bets was carrier volume 0. 5 cm ³ / g or more, favored properly is 0. 7 cm ³ / g or more, is preferred properly specific surface area 2 A heterogeneous catalyst of 50 m ² / g or more is desirable. These carriers adsorb transition metals and chlorine atoms derived from the polymerization catalyst. Further, if a heterogeneous catalyst having a particle size of 0.2 / m or more, that is, a catalyst substantially not containing a particle size of less than 0.2 // m is used, the filtration by filtration is difficult. It is preferable because the removal of the homogeneous catalyst is easy. If the particle size is too small, it is liable to leak at the time of filtration, and it is difficult to remove even by centrifugation, and the amount of transition metal atoms, which is a residue of the polymerization catalyst or the hydrogenation catalyst in the hydrogenated resin, increases. In addition, if filtration is performed using a filter with a small pore size to prevent leakage, clogging is likely to occur and work efficiency is poor.

 When a hydrogenation reaction is carried out using a supported catalyst such as nickel, palladium, or platinum, the reactivity can be increased by adding a small amount of alcohol such as isopropyl alcohol. The amount added is usually 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the solution.

Hydrogenation reaction solvent

The hydrogenation reaction is usually performed in an inert organic solvent. As the organic solvent, a hydrocarbon-based solvent is preferable, and among them, a cyclic hydrocarbon-based solvent having excellent solubility in the hydrogenated resin to be generated is particularly preferable. Specific examples include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as n-benzene and hexane, and cyclohexane and decalin. Examples include halogenated hydrocarbons such as alicyclic hydrocarbons, methylene dichloride, and dichloroethane, and a mixture of two or more of these can be used. When a solvent is used, the amount of the solvent used is usually 0.8 to 20 parts by weight, preferably 1 to 10 parts by weight based on 1 part by weight of the polymer.

 Usually, it may be the same as the polymerization reaction solvent, and the reaction may be performed by adding a hydrogenation catalyst or the like to the polymerization reaction solution as it is.

Hydrogenation reaction temperature

 The temperature of the hydrogenation reaction is usually at least 100, preferably from 120 to 300 ° C, more preferably from 140 to 250 ° C. If the hydrogenation reaction temperature is too low, the hydrogenation reaction does not proceed easily, and the hydrogenation rate does not increase sufficiently. If the temperature is too high, the polymer will be thermally degraded and operation will be difficult.

7 g force

Hydrogen pressure in the hydrogenation reaction is not particularly limited, usually, 1 0 to 20 0 kg / cm ^2, preferably 2 0-1 5 0 1 _5: 0 111 ^2, more preferably 3 0-1 0 0 a kg / cm ^2.

Catalyst removal

After the completion of the hydrogenation reaction, the catalyst may be removed by a conventional method such as centrifugation or filtration. 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. In the case of filtration, pressure filtration or suction filtration may be used. From the viewpoint of efficiency, it is preferable to use a filter aid such as diatomaceous earth or perlite. An adsorbent for a transition metal atom derived from a polymerization catalyst such as the above-mentioned carrier for a hydrogenation catalyst may be used as a filter aid. (Hydrogenated resin)

 The hydrogenation rate of the hydrogenated resin of the present invention is a rate at which the carbon-carbon double bond in the repeating unit is hydrogenated, and can be arbitrarily determined by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration, and the like. Can be adjusted. The hydrogenation rate is at least 90%, preferably at least 95%, more preferably at least 99%. When the hydrogenation rate of the hydrogenated resin is low, the stability to air oxidation is not sufficient, and it is particularly difficult to maintain the colorless and transparent properties required for optical materials.

 Usually, the repeating unit derived from a monomer other than the cyclopentadiene monomer is hydrogenated to substantially the same degree as the linear addition polymerization type repeating unit of the cyclopentadiene monomer. However, when an aromatic ring such as a fuynyl group is present in the resin structure, as in the case of using a styrene monomer, the hydrogenation catalyst is changed from a combination catalyst of a transition metal compound and an alkyl metal compound. By selection, the aromatic ring can be selectively left without hydrogenation. In that case, if the hydrogenation rate calculated excluding the unsaturated bond of the aromatic ring is within the above range, it can be used as the hydrogenated resin of the present invention. The aromatic ring has stability to air oxidation, but when higher stability is required, it is preferable to hydrogenate the aromatic ring.

 The hydrogenated resin of the present invention has a molecular weight range of 25 ° C., an intrinsic viscosity [] measured in toluene of 0.1 to 10 d 1 g, preferably 0.2 to 5 dl Z g. Preferably it is 0.3-2 dl / g. If the intrinsic viscosity of the hydrogenated resin is too small, the mechanical strength of the molded article will be low, and if the intrinsic viscosity is too large, the melt viscosity will be high and molding processing will be difficult.

The hydrogenated resin of the present invention is amorphous, transparent, low birefringent, and electrically insulating. It has excellent edge properties, usually has a Tg of 70 ° C or more, has low moisture absorption, has excellent electrical insulation properties, and has mechanical toughness.

In particular, a linear addition polymerization type repeating unit of a cyclopentadiene monomer is 10 to 50% by weight and a linear addition polymerization type repeating unit of a vinyl group-containing cyclic hydrocarbon monomer is 50 to 90%. % By weight of a copolymer having a Tg of 90 ° C. or more and a mechanical strength of at least 550 kgf cm ² in bending strength, preferably It is excellent at 600 kgf / cm ² or more, and more preferably at 600 kgf / cm ² or more.

 Similarly, 10 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and 50 to 90% by weight of a linear addition polymerization type repeating unit of a norbornene monomer. A resin obtained by hydrogenating a copolymer containing styrene usually has a Tg of 120 ° C. or higher, and has excellent mechanical strength.

 (Molding)

 The hydrogenated resin of the present invention can be molded by a conventional molding method, for example, injection molding, extrusion molding, compression molding, cast molding, inflation molding, blow molding and the like.

 (Additive)

Various additives may be added to the hydrogenated resin of the present invention, if desired. The additives used include, for example, phenol-based antioxidants, antistatic agents, ultraviolet absorbers, rubbery polymers, petroleum resins, and heterogeneous thermoplastic resins. In addition, for the purpose of improving moldability and physical properties, for example, fibrous fillers such as glass fiber and carbon fiber; and particulate fillers such as silica, alumina, talc, aluminum hydroxide, and calcium carbonate. Tetrakis [2- (3,5-di-tert-butyl-4-hydroxyhydroxy) ethylpropionate G) methane, 2,6-di-t-butyl-41-methylphenol and other antioxidants; etc., as well as light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, flame retardants, pigments, dyes, An anti-blocking agent or the like may be added. Generally, to avoid elution from the hydrogenated resin, these additives are preferred as having a higher molecular weight, and as the amount of addition is smaller, the more preferred.

 When a sheet is formed by a casting method, a leveling agent may be added to reduce the surface roughness. As the leveling agent, for example, a coating repelling agent such as a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, or a silicone-based leveling agent is used. Among them, those having good compatibility with the solvent are preferred.

 When a compounding agent is added to the hydrogenated resin of the present invention, the transparency generally decreases. However, when the compound is molded into a chemical container or the like, the transparency only needs to be sufficient to confirm the amount and state of the contents. Therefore, the required light transmittance is usually at least 40%, preferably at least 50%, measured in a wavelength range of 450 to 700 nm using a molded plate having a thickness of 2 mm. , More preferably 60% or more. When used as an optical material, the light transmittance is usually 80% or more, preferably 85%, measured at a wavelength of 400 to 80 nm using a 1.2 mm thick molded plate. The above is more preferably at least 88%, particularly preferably at least 90%.

Additives also affect the electrical properties of the hydrogenated resin, and additives that do not have a charging fanning effect reduce electrical properties. If a hydrogenated resin is used as the electrical insulating material, the volume resistivity is usually at least 10 ¹⁶ Q cm, preferably at least 5 x 10 ¹⁶ Ω cm, and the dielectric constant is 10 ^{2 H z, 1 0 6 H z} , 1 0 9 3 or less at any of frequencies H z, preferably Is 2. 5 or less, the dielectric loss ^{tangent, 1 0 2 H z, 1} 0 6 H z, 1 0 9 H z of 1 0_ ³ or less at any frequency, favored properly is 7 x 1 0- ⁴ below Nori.

 (Application)

 The hydrogenated resin of the present invention is useful in a wide range of fields as various molded articles including optical materials. For example, optical materials; electrical insulating materials; medical polymer materials; electronic component applications such as photodetector windows; IC carrier tapes, shippers, IC trays, wafer carriers, and ultrapure water piping. Parts processing equipment; Structural materials and building materials such as windows, equipment parts, and housing; Automotive equipment such as bumpers, room mirrors, headlamp power, tail lamp covers, instrument panels; Speaker cones, speakers It can be used for various uses such as vibration devices, electric equipment such as microwave oven containers, films, sheets, and helmets.

Optical materials

The hydrogenated resin of the present invention has transparency, low birefringence, a glass transition temperature (T g) of 70 ° C. or higher, low hygroscopicity, and mechanical toughness. For example, it is useful as an optical material such as an optical disk, an optical lens, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, a light guide plate, a polarizing film, and a phase difference film. The hydrogenated resin of the present invention has low adsorption of chemicals, particularly chemicals having polar groups such as alcohols, amines, esters, amides, ethers, carboxylic acids, and amino acids. In addition, since organic substances and the like contained as impurities in the resin are less likely to ooze out, they do not deteriorate even when contacted with chemicals. In addition, the resin solution is mixed with acidic water and pure It is used as a medical device because the residual amount of transition metal atoms and hydrogenation catalyst metal derived from the polymerization catalyst can be reduced to 1 ppm or less by repeatedly washing with water, etc. be able to

 Medical equipment includes, for example, liquid, powder or solid drug containers such as liquid drug containers for injection, ampoules, prefilled syringes, infusion bags, solid drug containers, eye drops containers, and infusion containers; food containers Sampling test tubes, blood collection tubes, sample containers such as sample containers for blood tests; Medical instruments such as syringes; Sterile containers such as scalpels, medical instruments such as forceps, gauze, and contact lenses; Beakers, Petri dishes , Flasks, test tubes, centrifuge tubes, etc. · Analytical instruments; medical optical components such as plastic lenses for medical tests; medical infusion tubes, piping, joints, valves and other piping materials; denture bases, Examples include artificial hearts, artificial organs such as artificial roots, and parts thereof.

 In particular, long-term storage of medicines, especially liquid medicines, prefill donges, sealed medicine bags, ophthalmic containers, ampules, vials, ophthalmic containers, etc. Compared to those, it has the favorable properties that there are no impurities, etc. eluted from the resin in addition to transparency, physical properties, etc., and that it does not adsorb chemicals, so that there is little alteration of chemicals.

Electrical insulation material

The hydrogenated CPD polymer of the present invention is useful in a wide range of fields as an electrical insulating material. For example, coating materials for electric wires and cables, consumer and industrial electronic equipment, OA equipment such as copiers 'computers' and printers, and general insulating materials such as instruments; rigid printed circuit boards, flexible printers Circuit boards such as printed circuit boards and multilayer printed circuit boards, especially High-frequency circuit boards for satellite communication equipment that require high-frequency characteristics; liquid crystal substrates ♦ Optical memory • Transparent conductive film base materials such as surface heating elements such as automobile and aircraft defrosters; transistors • ICs • LSIs Semiconductor sealing materials such as LEDs, parts; motors, connectors, switches * Encapsulation materials for electric and electronic parts, such as sensors; body materials, such as televisions and video cameras; parabolic antennas, flat antennas, radar It can be suitably used as a structural member of a dome.

 Example

 Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples. The methods for measuring physical properties are as follows.

 (1) Number average molecular weight: Measured by gel-permeation-chromatography using toluene as a solvent.

 (2) Intrinsic viscosity: Measured in toluene at 25.

 (3) Glass transition temperature (Tg): measured by the DSC method.

 (4) Retardation value: Measured by the double-pass method at a wavelength of 830 nm.

 (5) Flexural strength: Measured according to ASTM D-790.

 (6) The ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (Π) is J. Pollymer Sc, Part B4, 701 (1 9 6 6) Based on the method of Aso et al.

[Reference Example 1]

10 parts by weight of CPD and 90 parts by weight of toluene were placed in a glass-made reaction vessel purged with nitrogen, and cooled to 0 ° C. While stirring, 1 part by weight of a 20% by weight boron trifluoride getyl ether complex solution in toluene was added, and the mixture was allowed to react at 0 ° C. for 5 hours. The reaction solution was mixed with 500 parts by weight of The polymer was placed in propyl alcohol while stirring, and the precipitated polymer was collected and dried under reduced pressure of 1 torr or less for 24 hours to obtain 65 parts by weight of a colorless polymer. The intrinsic viscosity of this polymer was 0.52 dl / _g . Infrared spectroscopy shows that the intrinsic skeleton [77] is the same skeletal structure as that of a known CPD polymer (polymer chemistry, 7, 734, 1962) with a limiting viscosity of 0.06 dl / g. It was found that the polymer was composed of linear addition polymerization type repeating units of CPD. In the infrared spectroscopic scan Bae-vector, 3 0 4 0 cm- ¹ to H- C = bond, 7 5 0 c nr ¹ strong absorption based on C = C bond was observed, - NMR (black port At 30 ° C), at 5.6 ppm based on protons bound to unsaturated carbon with HC = CH— groups, l ~ 3 ppm based on protons bound to saturated carbon Absorption was observed at an intensity ratio of 2: 4. Also, the absorption of 1.3 to 1.8 ppm, 1.8 to 2.2 ppm, 2.2 to 3.O ppm is 31.9: 18.8: 49.3 The ratio of the repeating unit represented by the general formula (I) in the linear addition polymerization type repeating unit of the CPD monomer was 57% by weight.

 [Example 1]

30 parts by weight of the polymer obtained in Reference Example 1 was dissolved in 70 parts by weight of cyclohexane, and a nickel catalyst supported on alumina (0.3 part by weight of Nigel, 0.35 part by weight of nickel oxide, 1 part by weight of catalyst) . 2 parts by weight, the pore volume 0. 8 cm ³ / g, a specific surface area 3 0 0 m ² Z g) 1 part by weight and b Sopuro Piruaruko one le 2 parts by weight of, in auto click Leeb, 2 3 0 The reaction was performed at 50 ° C. and a hydrogen pressure of 50 kg / cm ² for 5 hours. After completion of the reaction, the nickel catalyst was removed by filtration, the reaction solution was stirred into 500 parts by weight of isopropyl alcohol, and the precipitated polymer was collected by filtration, and then filtered under reduced pressure of 1 t0 rr or less. Dry for 4 hours and remove 27 parts by weight of colorless hydrogenated resin. Obtained. This hydrogenated resin has an infrared spectroscopy spectrum of 30 40 cm " ¹ .

It was confirmed that the absorption at 750 cm- ¹ completely disappeared, the peak at 5.6 ppm also completely disappeared in ¹ H-NMR, and the hydrogenation rate was almost 100%. The intrinsic viscosity was 0.52 d 1 and the glass transition temperature was 79 C 0 "ο

 This hydrogenated resin was press-molded at 180 ° C, 2 mm thick, diameter

An 86 mm plate was made. The plate was colorless and transparent, and the light transmittance was 90.2% or more at wavelengths of 400 to 830 nm, and the retardation value was 20 nm or less. This hydrogenated resin was press-molded at 180 ° C to produce a disc having a thickness of 1.2 mm and a diameter of 12.5 cm. Was measured by using the circular扳volume resistivity of the resin is 5 X 1 0 ¹⁶ Ω cm or more on, also, any frequency of ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ H z Oite also respectively the dielectric constant and dielectric loss tangent, 2. was 3 4 and 5 X 1 0- ⁴ in.

 [Reference Example 2]

Boron trifluoride getyl ether complex 20 The colorless polymer was prepared in the same manner as in Reference Example 1 except that 5 parts by weight of 1% by weight of tungsten hexachloride was used instead of 1 part by weight of a toluene solution. 5 parts by weight were obtained. In this intrinsic viscosity of the polymer 0. 7 8 dl Z g, a infrared spectroscopy scan Bae-vector, 3 0 4 0 cm- ¹ to H- C = bond, C = C bond to 7 5 0 cm- ¹ NMR (at 30 ° C / 30 ° C) in NMR (at 5.6 ppm) — HC = CH 3 -proton bound to unsaturated carbon, l ~ 3 ppm Absorption based on the protons bound to the saturated carbon was observed at an intensity ratio of 2: 4. Also, the absorption of 1.3 to 1.8 ppm, 1.8 to 2.2 ppm, 2.2 to 3.O ppm is 26.6: 23.8: 49.6, and CPD Of linear addition polymerization type The repeating unit represented by the general formula (I) in the repeating unit was 53% by weight.

 [Example 2]

25 parts by weight of a colorless hydrogenated resin was obtained in the same manner as in Example 1 except that the polymer obtained in Reference Example 2 was used instead of the polymer obtained in Reference Example 1. In the hydrogenated resin, the absorptions at 3040 cm " ¹ and 7500 cm- ¹ were completely lost in the infrared spectroscopy spectrum, and the 樹脂 -NMR spectrum was 5.6 ppm. It was confirmed that the absorption had completely disappeared, and the hydrogenation ratio was approximately 100% The intrinsic viscosity was 0.76 d1 / g, and the glass transition temperature was 81 ° C.

 Furthermore, as a result of analyzing a 10% by weight hexane solution of the hydrogenated resin by using an atomic absorption spectrometer, the atomic weight of tungsten in the resin was less than 0.05 ppm (detection limit) and the atomic weight of nickel was less than 0.05 ppm. O lp pm (detection limit). In addition, 100 mg of this hydrogenated resin was burned in a Doman combustor, absorbed in 5 ml of pure water, and analyzed by iontophoresis.The chlorine atom content was 0.02 ppm (detection limit). )

 To 180 parts by weight of the hydrogenated resin was added 0.08 parts by weight of an antioxidant (manufactured by Ciba Geigy Co., Ltd., Irganox 11010), and a twin screw extruder (TEM manufactured by Toshiba Machine Co., Ltd.) — 35 B, screw diameter 37 mm, L / D = 32, screw rotation speed 250 rpm, resin temperature 215 ° C, feed rate 1 OkgZ time) Extruded and pelletized.

Using this pellet, injection molding (molding pressure: 350 tonnes, resin temperature: 225 C, mold temperature: 70 ° C), diameter: 20 Omm, height: 130 mm, average thickness: 3 mm A 2 mm-thick cylindrical transparent container and a 86 mm-diameter specimen were prepared. The test piece with a thickness of 2 mm is colorless and transparent, has a light transmittance of 90.3% or more at a wavelength of 400 to 8300 nm, a retardation value of 20 nm or less, and a turbidity of 0.1%. there were.

 2 in LB medium (adjusted aqueous solution of 1% by weight of pactrypton, 0.5% by weight of yeast tract, 1% by weight of NaC, and 0.1% by weight of glucose to pH 7.5) Add 1% by weight of agar, sterilize with steam for 30 minutes in 1 2 1 to gel, place 300 ml in a molded container before solidification, leave at room temperature for 6 hours, It was capped with foil and sterilized by irradiation with 7 lines at 25 kGy. After the treatment, the cells were incubated at 37 ° C for 3 days, but no fungal growth was observed. In addition, the appearance of the transparent container after the treatment was good, and no turbidity, cracking, or deformation was visually observed.

 The test piece was immersed in an aqueous sodium carbonate solution of PH9, hydrochloric acid of pH 4 and ethanol for 48 hours, and the appearance was observed, but there was no change, and there was no change in turbidity and light transmittance. .

 The test piece was cut into a 10 mm width, 20 g of the test piece was ultrasonically washed in distilled water for 20 minutes, and then dried at 40 ° C. for 10 hours. Next, this 200 g test piece was placed in a hard glass flask, and 200 g of distilled water was added. The bottle was covered with a hard glass lid and allowed to stand at 50 ° C for 24 hours to recover distilled water.

 As a control, 200 g of distilled water was placed in a hard glass flask, covered with a hard glass lid, and allowed to stand at 5 CTC for 24 hours.

The difference between the two types of distilled water, such as atomic absorption spectrometry, ion chromatography, and combustion-non-dispersive infrared gas analysis, was used to determine the amount of elution from the test piece. Below 0.05 ppm (detection limit), nickel atom elution amount is 0.01 ppm (detection limit) Below, the chlorine atom elution amount was below 0.02 ppm (detection limit), and the total organic carbon amount was below 2 ppm (detection limit).

 The above test pieces were subjected to an elution test according to the Japanese Pharmacopoeia No. 12 Revised "Plastic Test Method for Infusion". Foam disappears within 3 minutes, pH difference is -0.02, UV absorption is 0.05, and potassium permanganate reducing substance is 0.13 ml. It turned out to have suitable characteristics.

 [Reference Example 3]

In a reactor purged with nitrogen, 90 parts by weight of CPD, 100 parts by weight of methylstyrene, 300 parts by weight of toluene and 100 parts by weight of nitromethane were put, and cooled to zero. While stirring, 64 parts by weight of a 1.0% by weight solution of Pd (CH ₃ CN) ₄ (BF ₄ ) ₂ in nitromethane was added, and the mixture was reacted for 2 hours while keeping the reaction temperature at zero. The reaction solution was poured with stirring into 150 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid, and the precipitated polymer was collected by filtration and collected, and 300 parts by weight of methanol was added. after in washing to obtain 5 0 ^e C in the following reduced pressure 1 torr 2 4 hours dried 6 8 parts by weight colorless copolymers.

The intrinsic viscosity of this copolymer was 0.47 dl Zg. In the infrared spectroscopy spectrum, it's 3 0 4 0 ^! To! ! - Ji: bond, 7 5 0 cm- ¹ at a C = C-bond, 6 9 5 cm- ¹ absorption based on Fuweniru group observed et al is in, ¹ H- NM R 6. 4~ 7 in spectrum. The absorption based on phenyl group protons at lppm, unsaturated carbons at 5.6 ppm, and saturated carbons at 1-3 ppm is 4:30:66. Ratio was observed. The composition ratio between CPD and α-methylstyrene was calculated to be 95: 5 in molar ratio from the intensity ratio of 'Η-NMR. Also, 1.3-1.8 p p'm, 1.8-2.2 p pm, 2.2-3.0 p D m Is 2.3.5: 1.3.7: 62.8, and the repeating unit represented by the general formula (I) in the linear addition polymerization type repeating unit of the CPD monomer is , 47% by weight.

 [Example 3]

60 parts by weight of the copolymer obtained in Reference Example 3 was dissolved in 540 parts by weight of cyclohexane, and a palladium catalyst supported on alumina (E4L1, manufactured by Nippon Kagaku Co., 3% by weight of palladium supported) 3 parts by weight and 10 parts by weight of isopropyl alcohol were added, and reacted in an autoclave at 140 ° C. and a hydrogen pressure of 50 kgZcm ² for 5 hours. After completion of the reaction, the palladium catalyst was removed by filtration, and the reaction solution was poured into 190 parts by weight of methanol while stirring, and the precipitated polymer was collected by filtration. It was dried at 50 ° C under a reduced pressure of 1 Torr or less for 24 hours to obtain 55 parts by weight of a colorless hydrogenated resin.

The limiting viscosity of this hydrogenated resin was 0.47 d1 nog, and the glass transition temperature was 89 ° C. In the infrared spectroscopy spectrum, the absorption at 3040 cm "\ 750 cm- ¹ and 695 cm- ¹ completely disappeared, and the 'H-NMR spectrum also showed 6.4 to 7 lppm and 5. The absorption at 6 ppm completely disappeared, and it was confirmed that almost 100% of hydrogen was added to both the phenyl group and the unsaturated group of the cyclopentene ring.

This hydrogenated resin was press-molded at 200 ° C. to produce a flat plate having a thickness of 2 mm and a diameter of 86 mm, and a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The 2 mm-thick plate was colorless and transparent and tough. The light transmittance was 90.4% or more for wavelengths of 400 to 830 nm, and the letter daneyon value was 20 nm or less. The thickness 1. volume resistivity of the hydrogenation resin measured using a circular扳of 2 mm is 5 X 1 0 ¹⁶ Ω cm or more, the dielectric constant ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ in any of the frequency of the H z 2. 3 3 In, the dielectric loss tangent was also ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ 5 X in any of the frequency of the H z 1 0 -4.

 [Example 4]

 In the same manner as in Example 3 except that 60 parts by weight of CPD and 40 parts by weight of styrene were used instead of 90 parts by weight of CPD and 10 parts by weight of na-methylstyrene, 78 parts by weight of the copolymer was used. Obtained.

The intrinsic viscosity of this copolymer was 0.55 dl / g. In infra-red Hikarisupeku torr to ^{3 0 4 0 cm- 1 H- C} = binding and 7 5 0 cm one ¹ - C = C first binding, absorption based on Fuweniru group 6 9 5 cm- ¹ In the ¹ H—NMR spectrum, it was observed that 6.4 to 7.1 ppm of the fuunyl-based protein, 5.6 ppm of the unsaturated carbon-bonded proton, and 1-3 ppm of the saturated carbon. Absorption based on bound proteins was observed at an intensity ratio of 26: 20: 5. — From the NMR intensity ratio, the composition ratio of CPD to styrene was calculated to be 65:35 in molar ratio.

70 parts by weight of this copolymer was dissolved in 60 parts by weight of cyclohexane, and 3.5 parts by weight of the alumina-supported nickel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were used. Was added, and the mixture was reacted in an autoclave at 230 ° C. and a hydrogen pressure of 50 kg / cm ² for 5 hours. After completion of the reaction, the nickel catalyst was removed by filtration, and the reaction solution was poured into 220 parts by weight of methanol with stirring, and the precipitated resin was collected by filtration. Drying at 50 ° C under a reduced pressure of 1 torr or less for 24 hours gave 64 parts by weight of a colorless hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin is 0.54 d 1 / g and the glass transition temperature is 98. C. In the infrared spectrum, the absorptions at 3040 cm- ¹ ', 760 cm- ¹ and 695 cm- ¹ completely disappeared, and the H-NMR spectrum also showed 6.4-7. 5. Absorption of 6 ppm completely disappears, It was confirmed that almost 100% of hydrogen was added to both the phenyl group and the unsaturated group of the cyclopentene ring.

This hydrogenated resin was press-molded at 200 ° C. to form a flat plate having a thickness of 2 mm and a diameter of 86 mm, a circle having a thickness of 1.2 mm and a diameter of 12.5 cm. The 2 mm-thick plate was colorless, transparent and tough, with a light transmittance of 90.3% or more in the range of 400 to 80 nm, and a letter decision value of 20 nm or less. The thickness 1. volume resistivity of this tree fat was measured using a circular plate of 2 mm is 5 X 1 0 ¹⁶ Ω cm or more, the dielectric constant ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ H at 2.3 1 at any frequency z, Yuden loss tangent ^{1 0 2 H z, 1 0} 6 H z and 1 0 ^s 4 can have you to any of the frequency of the H 2 X 1 0- ^{Was 4} .

 [Example 5]

 Example 10 Except that instead of 90 parts by weight of CPD and 10 parts by weight of na-methylstyrene, 50 parts by weight of CPD, 20 parts by weight of a 50% by weight solution of isobutylene in toluene and 40 parts by weight of styrene were used. In the same manner as in 3, a copolymer (69 parts by weight) was obtained.

The intrinsic viscosity of this copolymer was 0.53 d 1 / g. In infra-red Hikarisupeku torr to ^{3 0 4 0 cm- 1 H- C} = bond and 7 5 0 cm- ¹ at a C = C-bond, is absorption based on Fuweniru group 6 9 5 cm- ^{1 1} H-NMR spectra showed 6.4 to 7.1 ppm of phenyl group protons, 5.6 ppm of protons bound to unsaturated carbon, and 1-3 ppm to saturated carbon. Absorption based on the selected protons was observed at an intensity ratio of 20:17:63. The composition ratio of CPD: isobutylene: styrene was calculated to be 57:15:27 in molar ratio from the '-NMR intensity ratio.

Dissolve 60 parts by weight of this copolymer in 540 parts by weight of cyclohexane, Further, 3.0 parts by weight of the alumina-supported Nigel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were added, and hydrogenation was carried out in the same manner as in Example 4, and 56 parts by weight of the hydrogenated resin was added. Obtained.

The limiting viscosity of this hydrogenated resin is 0.5 d 1 ng and the glass transition temperature is 84. C. In the infrared spectroscopy spectrum, the absorptions at 3040 cm- \ 760 cm- ¹ and 695 cm- ¹ completely disappeared, and even in the ¹ H-NMR spectrum, 6.4 ~ 7 lppm and The absorption at 5.6 ppm completely disappeared, confirming that almost 100% of hydrogen was added to both the phenyl group and the unsaturated group of the cyclopentene ring.

 This hydrogenated resin was press-molded at 200 ° C. to produce a flat plate having a thickness of 2 mm and a diameter of 86 mm. The plate was colorless, transparent and tough, had a light transmittance of 90.5% or more in the range of 400 to 830 nm, and a retardation value of 20 nm or less.

 [Example 6]

 Instead of 90 parts by weight of C P D and 10 parts by weight of α-methylstyrene,

54 parts by weight of a copolymer was obtained in the same manner as in Example 3 except that 90 parts by weight of CPD and 10 parts by weight of dipentene were used.

The intrinsic viscosity of this copolymer, 0.1 was 3 1 dl "g. In infra-red Hikarisupeku torr to ^{3 0 4 0 cm- 1 H- C} = binding and 7 5 0 cm- ¹ — Absorption due to C = C-bond was observed.11 In the NMR spectrum, a protein bonded to unsaturated carbon at 5.6 ppm and a protein bonded to saturated carbon at l to 3 ppm based emission absorption 2 9:. 7 was observed at 1 intensity ratio ¹ H- composition ratio from the intensity ratio of the CPD and dipentene the NMR 9 in a molar ratio of 5: was calculated to 5.

50 parts by weight of this copolymer was dissolved in 540 parts by weight of cyclohexane, and 3.0 parts by weight of the nickel-supported nickel catalyst used in Example 1 was further dissolved. Then, 10 parts by weight of isopropyl alcohol was added, and hydrogenation was carried out in the same manner as in Example 4 to obtain 43 parts by weight of a hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin is 0.31 d 1 / and the glass transition temperature is 87. C. In the infrared spectroscopy spectrum, the absorptions at 340 cm- ¹ and 760 cm- ¹ completely disappeared, and in the ¹ H-NMR spectrum, the absorption at 5.6 ppm disappeared completely. It was also confirmed that almost 100% of the unsaturated groups of the cyclopentene ring and the cyclohexene ring were hydrogenated.

 This hydrogenated resin was press-molded at 200 ° C. to produce a flat plate having a thickness of 2 mm and a diameter of 86 mm. The plate was colorless and transparent, and had a light transmittance of 90.5% or more at a wavelength of 400 to 80 nm and a retardation value of 2 Onm or less.

 [Example 7]

 In the same manner as in Example 3 except that 50 parts by weight of CPD and 50 parts by weight of norbornene were used instead of 90 parts by weight of CPD and 10 parts by weight of Obtained.

The intrinsic viscosity of this copolymer was 0.46 dl / g. The infra-red Hikarisupeku H- C = bond and 7 5 0 cm- ¹ to 3 0 4 0 cm- ¹ in Torr - C = C-based coupling absorption was observed, - in NMR spectrum The absorption based on the proton bound to unsaturated carbon at 5.6 ppm and the absorption based on the proton bound to saturated carbon at l to 3 ppm was observed at an intensity ratio of 18:82. — From the NMR intensity ratio, the composition ratio of CPD to norbornene was calculated to be 66:34 in molar ratio.

60 parts by weight of this copolymer was dissolved in 540 parts by weight of cyclohexane, and 3.0 parts by weight of the alumina-supported Nigel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were further dissolved. In addition, as in Example 4, To obtain 56 parts by weight of a hydrogenated resin.

The intrinsic viscosity of the hydrogenated resin was 0.46 d1 g, and the glass transition temperature was 16.5 ° C. In the infrared spectroscopy spectrum, the absorptions at 340 cm- ¹ and 760 cm- ¹ disappeared completely, and in the NMR spectrum the absorption at 5.6 ppm disappeared completely. It was confirmed that about 100% of the unsaturated group of the cyclopentene ring was hydrogenated.

This hydrogenated resin was press-molded at 200 to produce a flat plate having a thickness of 2 mm and a diameter of 86 mm, and a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The 2 mm thick flat plate was colorless and transparent and tough, with a light transmittance of 90.5% or more at wavelengths of 400 to 830 nm and a retardation value of 20 nm or less. The thickness 1. volume resistivity of the resin was measured using a circular plate of 2 mm is 5 X 1 0 ¹⁶ Ω cm or more, the dielectric constant ^{1 0 2 H z, 1 0} 6 H z and 1 0 in 2.3 3 in any of the frequency of ⁹ H z, Yuden loss tangent ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ 4 can have you to any frequency of the H z X 1 0- ⁴ Met.

 [Example 8]

 A nitrogen-substituted glass reaction vessel was charged with 60 parts by weight of CPD, 40 parts by weight of α-methylstyrene, and 900 parts by weight of toluene, and cooled to 178 ° C. While stirring, 10 parts by weight of a 20% by weight toluene solution of boron trifluoride getyl ether complex was added, and the mixture was allowed to react at a temperature of not more than 75 ° C. for 5 hours. The reaction solution was put into 500 parts by weight of isopropyl alcohol with stirring, and the precipitated polymer was collected by filtration and dried under a reduced pressure of I mmHg or less for 24 hours to obtain 83 parts by weight of the polymer. A colorless linear addition polymerization type copolymer was obtained.

The intrinsic viscosity of the copolymer measured in toluene at 25 ° C. was 0.37 dl /. To 3 0 4 0 cm- ¹ in the infrared spectral scan Bae-vector H- C = Binding, and 7 5 0 cm- ¹ at a C = C first binding, absorption was observed based on Fuweniru group 6 9 5 cm- ^{1. In the 1} H-NMR spectrum, 6.4 to 7.1 ppm of phenyl group protons, 5.6 ppm of protons bonded to unsaturated carbon, and 1 to 3 ppm of protons bonded to saturated carbon. a peak based on tons 28: 1 _4: was observed at 5 7 intensity ratio. From the intensity ratio of the 'H-NMR spectrum, the composition ratio of CPD to styrene was calculated to be 65:35 in molar ratio.

 Hydrogenation was carried out in the same manner as in Example 1 except that this copolymer was used instead of the polymer obtained in Reference Example 1, to obtain 29 parts by weight of a colorless hydrogenated resin.

The hydrogenation resin, the absorption of infrared spectroscopy scan Bae-vector of 3040 cm- 750 cm ^"1 and 69 5 c nr ^1, 6. in ¹ H- NMR spectra 4 to 7. LPPM and 5 The complete disappearance of the 6 ppm peak confirmed that the hydrogenation rate was 100% The limiting viscosity of this hydrogenated resin measured in toluene at 25 ° C was 0. 38 dl / g and Tg were 122 ° C.

 When this hydrogenated resin was dissolved in cyclohexane and analyzed, the atomic mass of boron was less than 0.5 ppm (detection limit), the mass of nickel was less than 0.0 lp pm (detection limit), The chlorine atomic weight was less than 0.02 ppm (detection limit).

 This hydrogenated resin was pelletized in the same manner as in Reference Example 3 except that the resin temperature was set at 260 ° C.

 Using this pellet, injection molding (molding pressure: 350 tonnes, resin temperature: 26.5 ° C, mold temperature: 100 ° C) was performed, and a cylindrical transparent material was used as in Example 2. A container and a test piece with a thickness of 2 mm and a diameter of 86 mm were prepared.

When the light transmittance of the test piece was measured, the wavelength was 400 to 8300 nm. At 90.7% or more, the transparency was good. The turbidity was measured to be 0.08%.

 As in Example 1, 300 ml of LB medium supplemented with 2% by weight of agar was placed in a molded container, and one of the test pieces was placed. C, steam sterilization was performed for 30 minutes.

 After the treatment, the cells were kept at 37 ° C for 3 days, but no fungal growth was observed. The appearance of the transparent container after the treatment was good, and no turbidity, cracking, or deformation due to heat was visually observed.

 The turbidity measured after removing the LB medium solidified with agar from the test piece taken out of the container was 0.1%, and the total light transmittance was 89.8%.

 After immersion of the test piece in an aqueous solution of sodium carbonate at pH 9 and hydrochloric acid and ethanol at pH 4 for 48 hours, there was no change in appearance, and there was no change in turbidity or light transmittance.

Cut test piece 1 0 mm wide, washed 2 0 minutes監超waves to 2 0 g in distilled water and dried 1 0 h 4 0 ^e C. The test piece of 20 g was placed in a hard glass flask, and 200 g of distilled water was added. With a hard glass lid, steam sterilization was performed at 120 ° C. for 1 hour, cooled to room temperature, and allowed to stand for 24 hours to recover distilled water.

 As a control, 200 g of distilled water was placed in a hard glass flask, covered with a hard glass lid, steam-sterilized at 120 ° C for 1 hour, cooled to room temperature, and allowed to stand for 24 hours. After that, distilled water was collected.

The elution amount from the test piece was calculated from the difference between the two types of distilled water analysis results. The boron atom elution amount was 0.5 ppm (detection limit) or less, and the nickel atom elution amount was 0.01 ppm. (Detection limit) or less, chlorine atom The elution amount was less than 0.02 ppm (detection limit), and the total amount of organic carbon was less than 2 ppm (detection limit).

 As in Example 1, an eluate test was performed according to the Japanese Pharmacopoeia. The foaming disappeared within 3 minutes, the pH difference was -0.03, the ultraviolet absorption was 0.006, and the potassium permanganate reducing substance was 0.13 ml.

 [Comparative Example 1]

60 polymer parts of the CPD polymer obtained in the same manner as in Reference Example 1 were dissolved in 540 polymer parts of cyclohexane, and 6 polymer parts of the same palladium catalyst used in Example 3 were added. ° C. The reaction was carried out at a hydrogen pressure of 50 kg / cm ² for 15 hours. The hydrogenated resin was recovered in the same manner as in Example 3 to obtain 53 parts by weight of the hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin was 0.53 d 1 g, and the glass transition temperature was 80 ° C. In the infrared spectrum, the absorptions at 3040 cm- ¹ and 760 cm- ¹ decreased in intensity but did not disappear, and — 5.6 ppm absorption did not completely disappear even in the NMR spectrum. The absorption intensity ratio of 5.6 111 to 1 to 3 ppm was observed at an intensity ratio of 5:95, and the hydrogenation rate was 81%.

 An attempt was made to pelletize this hydrogenated resin in the same manner as in Example 2, but the coloring and burning were so severe that pelletization was not possible.

The hydrogenated resin was pressed at 1 8 0 ^e C, thickness 2 mm, was prepared a plate having a diameter of 8 6 mm. Although the board was tough, it was yellow and colored, and the outer periphery was strongly colored. The light transmittance of the relatively light-colored portion at the inner periphery was 89.0%, and the retardation value was 28 nm or less. When this molded plate was left in the air at room temperature for 3 weeks, the toughness was reduced and it became brittle.

[Comparative Example 2] 90 parts by weight of formaldehyde in place of 90 parts by weight of toluene in Reference Example 1, and titanium tetrachloride in place of 1 part by weight of a 20% by weight solution of boron trifluoride-ethylester complex in toluene. 7.1 parts by weight of a CPD polymer was obtained in the same manner as in Reference Example 1, except that 2.5 parts by weight of a 10% by weight toluene solution was used. The intrinsic viscosity of this polymer was 0.07 dl / g. In infrared spectroscopy scan Bae-vector based on 3 0 4 0 cm- ¹ to H- C = bond and 7 5 0 cm- ¹ at a C = C conjoining absorption was observed, 5 in ¹ H- NMR spectrum Absorption based on unsaturated carbon bound at 6 ppm and saturated carbon bound at 1-3 ppm was observed at an intensity ratio of 2: 4.

 Hydrogenation was carried out in the same manner as in Example 1 except that this polymer was used instead of the polymer obtained in Reference Example 1, to obtain 2.7 parts by weight of a hydrogenated resin.

The limiting viscosity of this hydrogenated resin was 0.07 d 1 g, and the glass transition temperature was 78 ° C. Absorption at 3040 cm- ¹ and 760 cm- ¹ completely disappeared in the infrared spectroscopy spectrum, and absorption at 5.6 ppm disappeared completely in the NMR spectrum, and the cyclopentene ring was unsaturated. It was confirmed that the group was almost 100% hydrogenated. This polymer was press-molded at 180 to produce a flat plate having a thickness of 2 mm and a diameter of 86 mm, but it was very brittle and it was difficult to prepare the plate.

 [Reference Example 4]

70 parts by weight of styrene, 30 parts by weight of CPD, and 400 parts by weight of toluene were placed in a reactor purged with nitrogen, and cooled to 160 ° C. With stirring La, added Toruen solution 1 2 parts by weight of the concentration of 1.0 wt% of \ ^ Ji 1 _6, was reacted for 2 hours while maintaining the reaction temperature at a 6 0 ° C. The reaction solution was stirred in 150 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid. The precipitated copolymer was collected by filtration, washed with 300 parts by weight of methanol, dried at 50 V under a reduced pressure of 1 torr or less for 24 hours, and then subjected to 53 parts by weight of copolymer. A coalescence was obtained.

The intrinsic viscosity of this copolymer was 0.52 d. In infrared spectroscopic spectrum 3 0 4 0 cm- ¹ to H- C = bond, 7 5 0 cm- ¹ - C = C- bond, and 6 9 5 cm- absorption observed et based on Fuweniru group ¹ In the ¹ H—NMR spectrum, 6.4 to 7.1 ppm of protons of a phenyl group, 5.6 ppm of protons bound to unsaturated carbon, and 1 to 3 ppm of protons bound to saturated carbon Based absorption was observed at an intensity ratio of 36:14:50. Calculated from the intensity ratio of ¹ H-NMR, the composition ratio of styrene to CPD was 51:49 in molar ratio and 62:38 in weight ratio. Also, from the results of Reference Example 2, the weight ratio of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (Π) in this copolymer was 53:47. Is estimated.

 [Example 9]

50 parts by weight of the copolymer obtained in Reference Example 4 was dissolved in 450 parts by weight of cyclohexane, and a nickel catalyst supported on alumina (0.3 part by weight of nickel, 1 part by weight of catalyst, nickel oxide, 0.2 parts by weight, the pore volume 0. 8 cm ³ Z g, a specific surface area 3 0 0 m ² Z g) 3 parts by weight of isopropyl alcohol 1 0 parts by weight of, in Haut Useful Loew, 2 3 0. C, The reaction was carried out at a hydrogen pressure of 50 kcm ² for 5 hours. After completion of the reaction, the nickel catalyst was removed by filtration, and the reaction solution was poured into 2000 parts by weight of methanol while stirring, and the precipitated resin was collected by filtration. It was dried at 90 ° C. under a reduced pressure of 1 t 0 rr or less for 48 hours to obtain 44 parts by weight of a colorless hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin is 0.52 dl / g and the glass transition The temperature was 105 ° C. Further, the infrared spectroscopic scan Bae-vector, the absorption of the 3040 cnr ¹ 7 5 0 cm- ¹ and 6 9 5 cm- ¹ disappeared completely, 6. in 'H- NMR spectra 4 to 7. LPPM and The absorption at 5.6 ppm completely disappeared, and it was confirmed that almost 100% of the phenyl group and the unsaturated group in the pentene ring of the mouth were hydrogenated.

 Further, as a result of analyzing a 10% by weight solution of the hydrogenated resin in cyclohexane by atomic absorption spectroscopy, the atomic weight of tungsten in the polymer was 0.05 ppm (detection limit) or less, and the atomic weight of nickel was 0.05 ppm. pm (detection limit). In addition, 100 mg of this hydrogenated resin was burned in a Doman combustor, absorbed in 5 ml of pure water, and analyzed by iontophoresis.The chlorine atom weight was 0.02 ppm (detection limit). )

This hydrogenated resin was press-molded at 180 ° C to prepare a test plate A with a thickness of 1.2 mm and a diameter of 100 mm and a test plate B with a thickness of 2.0 mm and a diameter of 100 mm. did. Test plate A was colorless and transparent, had a light transmittance of 90.1% or more at a wavelength of 400 to 80 nm, and a birefringence value of 25 nm or less. Was measured using a test plate A, a volume resistivity of 5 X 1 0 ¹⁶ Q cm or more, in any of the 1 0 ² H z, 1 0 the frequency of the ⁶ H z and 1 0 ^beta Eta z, and the dielectric constant each dielectric loss tangent 2.4 0 and 5 x 1 0- ⁴ der ivy. A plate having a length of 6 O mm and a width of 12 mm was prepared by cutting the test plate Β, and the bending strength was measured to be 760 kgZ cm ² . These facts indicate that this hydrogenated resin is suitable as an optical material and an electrical insulating material.

 [Reference Example 5]

In a reactor purged with nitrogen, 100 parts by weight of CPD, 300 parts by weight of toluene, and 100 parts by weight of nitromethane were put, and cooled to o ° c. Stir While, the addition of concentration 1.0 wt% of _{P d (CH 3 CN) (} BF 4) 2 of the two-Toro methane solution 6 4 parts by weight, the reaction temperature was reacted between 2:00 while maintaining at 0. The reaction solution was poured into 150 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid while stirring, and the precipitated polymer was collected by filtration, washed, and washed with 300 parts by weight of methanol. Drying at 50 ° C under a reduced pressure of 1 torr or less for 24 hours gave 65 parts by weight of a colorless polymer.

The intrinsic viscosity of this polymer was 0.41 dl Zg. In infrared spectroscopy spectrum in ^{3 0 4 0 cm- 1 H- C} = bond, 7 5 0 cm- ¹ accepted absorption according to one C = C conjoining, 'H- NMR spectrum At 5.6 ppm, absorptions due to protons bound to unsaturated carbon and l to 3 ppm due to protons bound to saturated carbon were observed at an intensity ratio of 2: 4. The absorption of 1.3 to 1.8 ppm, 1.8 to 2.2 ppm, 2.2 to 3.O ppm is 23.5: 13.7: 62.8, and Aso Calculated based on the method described in the above, the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (Π) were found to have a weight ratio of 47:53.

 [Reference Example 6]

40 parts by weight of styrene, 30 parts by weight of methyl styrene, 30 parts by weight of CPD, 300 parts by weight of toluene, and 100 parts by weight of nitromethane were put into a reactor purged with nitrogen, and 0 ° C And cooled. While stirring, 64 parts by weight of a 1.0% by weight solution of Pd (CH ₃ CN) (BF ₄ ) ₂ in nitromethane was added, and the mixture was reacted for 2 hours while maintaining the reaction temperature at 0 ° C. The reaction solution was poured with stirring into 150 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid, and the precipitated polymer was collected by filtration and collected, and 300 parts by weight of methanol was added. After washing, it was dried at 50 ° C under a reduced pressure of 1 t0 rr or less for 24 hours to obtain 43 parts by weight of a copolymer. The intrinsic viscosity of this copolymer was 0.43 d 1 / g. In infrared spectroscopic spectrum 3 0 4 0 cm- ¹ to H - C = bond, 7 5 0 cm- ¹ at a C = C-bond, and 6 9 5 cm- ¹ absorption based on Fuweniru group The ¹ H-NMR spectrum showed that 6.4 to 7. lp pm of a phenyl group proton, 5.6 ppm of a proton bonded to an unsaturated carbon, and 1 to 3 ppm of a saturated carbon Absorption based on the protons bound to the A was observed at an intensity ratio of 31 _: 1: 5: 54. Calculated from the intensity ratio of Η-NMR, the composition ratio of styrene: na-methylstyrene: CPD was 29:16:55 in molar ratio, and 35:22:43 in weight ratio. Also, from the results of Reference Example 5, the weight ratio of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (Π) in this copolymer is 47:53. Can be estimated.

 [Example 10]

 40 parts by weight of the copolymer obtained in Reference Example 6 was dissolved in 360 parts by weight of cyclohexane, and 2.4 parts by weight of the same nickel catalyst used in Example 9 and 8 parts by weight of isopropyl alcohol were used. And a hydrogenation reaction was carried out in the same manner as in Example 9. After completion of the reaction, coagulation, separation and drying were carried out in the same manner as in Example 9 to obtain 36 parts by weight of a colorless hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin is 0.44 d 1 / g and the glass transition temperature is 120. C In infrared spectroscopy scan Bae-vector ^{3 0 4 0 cm- 1, 7} 5 0 cm- 1, and 6 9 5 cm- ¹ absorption disappeared completely, ¹ H - NMR spectrum in Torr 6.4 to 7 The absorptions at 1 ppm and 5.6 ppm completely disappeared, and it was confirmed that almost 100% of the phenyl group and the unsaturated group of the pentene ring were hydrogenated.

This hydrogenated resin was press-molded at 190 ° C., a test plate was prepared in the same manner as in Example 9, and the physical properties were measured. Light transmittance is wavelength 400-830 nm In 9 0.1% or more, the birefringence value is 2 5 nm or less, a volume resistivity of 5 xl 0 ¹⁶ Q cm or more, 1 0 ^{2 H z, 1 0 6 H} z and 1 0 ⁹ H z frequency in any case, each of the dielectric constant and dielectric loss tangent 2.3 5,5 1 0 ^4, the bending strength was 7 1 0 kg Bruno cm ^2. Thus, this hydrogenated resin is suitable as an optical material and an electrical insulating material.

 [Reference Example 7]

 In the same manner as in Reference Example 6, except that 30 parts by weight of α-methylstyrene was replaced by 30 parts by weight of 1-methyl-4-isoprobenylcyclohexene, a weight of 35 parts by weight was obtained. A coalescence was obtained.

The intrinsic viscosity of this copolymer was 0.45 d 1. The infrared spectroscopic spectrum 3 0 4 0 c πΓ to ¹ H- C = bond, and ^{7 5 0 c πτ 1 - C} = C conjoining, and 6 9 5 cm- ¹ absorption based on Fuweniru group ¹ H-NMR spectra showed 6.4 to 7.1 ppm of phenyl group protons, 5.6 ppm of protons bound to unsaturated carbon, and 1-3 ppm to saturated carbon. Absorption based on the selected protons was observed at an intensity ratio of 24:16:60. 'The composition ratio of styrene: 1-methyl-41-isoproveninolecyclohexene: CPD calculated from the H-NMR intensity ratio is 35: 8: 57 in molar ratio, and 43 in weight ratio: 1 3: 4 4 From the results of Reference Example 5, the weight ratio of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (Π) in the copolymer is 47:53. Can be estimated.

 [Example 11]

30 parts by weight of the copolymer obtained in Reference Example 7 was dissolved in 70 parts by weight of cyclohexane, and 1.8 parts by weight of the same nickel catalyst as used in Example 9 and 6 parts by weight of isopropyl alcohol As in Example 9 To perform a hydrogenation reaction. After completion of the reaction, solidification, separation and drying were performed in the same manner as in Example 9 to obtain 26 parts by weight of a colorless hydrogenated resin.

The intrinsic viscosity of this hydrogenated resin was 0.45 d 1 / g, and the glass transition temperature was 108 ° C. Absorption at 340 cm—750 cm- \ and 695 cm— ¹ disappeared completely in the infrared spectroscopy spectrum, and-6.4 to 7. lppm and 5.6 ppm in the NMR spectrum Completely disappeared, and it was confirmed that almost 100% of the unsaturated groups of the phenyl group, cyclohexene ring and cyclopentene ring were hydrogenated.

The hydrogenated resin was pressed at 1 8 0 ^e C, prepared in the same manner as in test plate as in Example 9, was measuring physical properties. Light transmittance wavelength from 400 to 830 nm with 9 0.2% or more, the birefringence value is 2 5 nm or less, a volume resistivity of 5 xl 0 ¹⁶ Q cm or ^{more, 1 0 2 H z, 1} 0 6 H z and in any of the frequency of 1 0 ⁹ H z, respectively the dielectric constant and dielectric loss tangent 2.3 5,5 1 0_ ^4, the bending strength was 7 ² 0 kgcm 2. This indicates that this hydrogenated resin is suitable as an optical material and an electrical insulating material.

 [Comparative Example 3]

 100 parts by weight of styrene, 200 parts by weight of toluene and 0.01 part by weight of azoisobutyronitrile are placed in a reactor purged with nitrogen, heated to a temperature of 80 ° C with stirring, and reacted for 10 hours. I let it. The resulting polymer solution was diluted by adding 500 parts by weight of toluene, and poured into 250 parts by weight of methanol with stirring, and the precipitated polymer was collected by filtration. It was dried at 70 ° C under a reduced pressure of 1 torr or less for 48 hours to obtain 92 parts by weight of polystyrene.

The intrinsic viscosity of this polystyrene was 0.74 d1 nog, and the glass transition temperature was 100 ° C. This polystyrene (50 parts by weight) was dissolved in tetrahydrofuran (450 parts by weight), and the same alumina-supported Nigel catalyst used in Example 9 (5 parts by weight) was added. and at a hydrogen pressure of 5 0 k gZ 0 111 ² reacted 1 0 hours. After completion of the reaction, the nickel catalyst was removed by filtration, and the reaction solution was poured into 2000 parts by weight of methanol with stirring, and the precipitated polymer was collected by filtration. 9 0 was obtained ^e C in 1 t 0 rr dried 48 hours at a reduced pressure of not more than 4 1 part by weight colorless polystyrene Hydrogen additives.

This hydrogenated polystyrene was press-molded at 190 ° C., a test plate was prepared in the same manner as in Example 9, and the physical properties were measured. Light transmittance wavelength 40 0 ~ 8 3 0 nm 9 0.1% or more, the birefringence value is 2 5 nm or less, the volume-specific resistance value of 5 X 1 0 ¹⁶ Ω cm or more, 1 0 ² H z, in any of the frequencies 1 0 ⁶ H z and 1 0 ⁹ H z also the dielectric constant and dielectric loss tangent were respectively 2.3 6 with 5 X 1 0- ^4. However, the test plate has low mechanical strength, easy Re split, flexural strength was 4 0 0 k gZ cm ^2.

 [Example 12]

 To 40 parts by weight of the hydrogenated resin obtained in Example 9 was added 0.02 parts by weight of an antioxidant (manufactured by Ciba-Gai Gi Co., Ltd., Irganox 100), and a twin-screw extruder (Toshiba Machine Co., Ltd.) Extruded at TEM-35B, screw diameter 35 mm, screw rotation speed 150 rpm, resin temperature 200 ° C).

Using this pellet, injection molding (made by Toshiba Machine Co., Ltd., IS-350FB-119AP, mold clamping pressure 350 tons, resin temperature 300.C, mold temperature 80 ° C) was performed. A test piece C having a diameter of 130 mm and a thickness of 1.2 mm and a cylindrical transparent container D having a diameter of 200 mm, a height of 130 mm and an average thickness of 3 mm were prepared. [Example 13]

 2% by weight agar was added to the LB medium, and the mixture was sterilized by steam at 121 ° C for 30 minutes to form a gel. Before solidification, 300 ml of the container was molded in Example 12 It was placed in D, allowed to stand at room temperature for 6 hours, covered with aluminum foil, and sterilized by irradiating it with 25 kGy. The appearance of the container after the treatment was good, and no cloudiness, cracking, or deformation was observed. After that, the cells were incubated at 37 for 3 days, but no fungal growth was observed.

 The test plate C formed in Example 12 was cut to a width of 10 mm, washed ultrasonically in distilled water for 20 minutes, and then dried at 40 ° C for 10 hours. This test plate is referred to as test plate E. The test plate E was subjected to an elution test according to the Japanese Pharmacopoeia No. 12 Revised "Plastic Test Method for Infusion". Foam disappears within 3 minutes, pH difference is 0.01, UV absorbance is 0.004, potassium permanganate reducing substance 0.16 ml, suitable for medical use It was found to have properties.

 [Example 14]

 Specimen C prepared in Example 12 was subjected to 70% nitric acid, phosphoric acid, hydrofluoric acid (hydrofluoric acid 7% by weight, nitric acid 42% by weight, water 51%), 37% hydrochloric acid, 30% diluted Sulfuric acid, concentrated sulfuric acid, 30% hydrogen peroxide aqueous solution, potassium hydroxide saturated aqueous solution, 29% ammonia water, acetone, isopropyl alcohol, trichloroethylene, 2.38% by weight tetramethylammonium The specimens were immersed in an aqueous solution of Demoxide and an etching solution for aluminum (80% by weight of concentrated phosphoric acid, 5% by weight of nitric acid, 5% by weight of glacial acetic acid, and 10% by weight of water) for 5 minutes. Specimen C swelled with trifluoroethylene and darkened with concentrated sulfuric acid, but was not affected by other chemicals, indicating good chemical resistance.

Place 200 g of test plate E in a hard glass container, and add 200 g of distilled water. Was. When covered with a hard glass lid and immersed for 24 hours at 80 ° C, the extracted organic matter was 3 X 10 ² / gZm ² per day in total organic carbon content. After that, when the same test piece was immersed again in 200 g of distilled water at 80 ° C for 144 hours, the amount of total organic carbon extracted was below the measurement limit per day.

 From these results, it was found that the polymer of the present invention had characteristics suitable as an electronic component processing equipment.

 [Reference Example 8]

A nitrogen-purged reactor norbornene 6 5 parts by weight, CPD 3 5 parts by weight, put toluene 3 0 0 parts by weight and Nitorome Tan 1 0 0 parts by weight, was cooled to 0 ^e C. While stirring, added concentration 1.0 wt% of _{P d (CHsCN) 4 (B} F4) 2 in nitromethane solution 6 4 parts by weight, was allowed to react for 2 hours while maintaining the reaction temperature at 0 ^e C. The reaction solution was poured with stirring into 150 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid, and the precipitated polymer was collected by filtration and collected, and then mixed with 300 parts by weight of methanol. After washing, the mixture was dried at 50 under reduced pressure of 1 torr or less for 24 hours to obtain 73 parts by weight of a copolymer.

The intrinsic viscosity of this copolymer was 0.45 d1 Zg. Infrared spectroscopy The spectral 3 0 4 0 c πτ to ¹ H- C = bond, 7 5 0 cm- ¹ at a C = C-based coupling absorption was observed, ¹ H- NMR spectrum At 5.6 ppm, absorptions based on protons bound to unsaturated carbon and l to 3 ppm based on protons bound to saturated carbon were observed at an intensity ratio of 12:88. ^{From the 1} H-NMR intensity ratio, the composition ratio of norbornene and CPD was estimated to be 51:49 in molar ratio and 47:53 in weight ratio.

[Example 15] ■ 70 parts by weight of the copolymer obtained in Reference Example 8 was dissolved in 60 parts by weight of cyclohexane, and a nickel catalyst supported on alumina (1 part by weight of catalyst, 35 parts by weight of nickel, 0.2 parts by weight of nickel oxide) Parts, pore volume 0.8 cm ³ / g.Specific surface area 300 m ² / g) 3 parts by weight and 12 parts by weight of isopropyl alcohol are added, and in an autoclave, 230 ° C, hydrogen pressure 50 kg Z cm ² For 5 hours. After completion of the reaction, the nickel catalyst was removed by filtration, and the reaction solution was poured into 280 parts by weight of methanol with stirring, and the precipitated polymer was collected by filtration. It was dried at 90 ° C. under a reduced pressure of 1 t 0 rr or less for 48 hours to obtain 65 parts by weight of a colorless hydrogenated resin.

The intrinsic viscosity of the hydrogenated resin was 0.45 d1 g, and the glass transition temperature was 199 ° C. Absorption at 340 cm- ¹ and 750 cm- ¹ disappeared completely in the infrared spectroscopy spectrum, and 5.6 ppm absorption also disappeared completely in the NMR-NMR spectrum However, it was confirmed that approximately 100% of the unsaturated group of the cyclopentene ring was hydrogenated.

 Furthermore, as a result of analyzing a 10% by weight cyclohexane solution of the hydrogenated resin by atomic absorption spectrometry, the atomic weight of palladium in the hydrogenated resin was 0.05 ppm (detection limit) or less, and the atomic weight of nickel was 0%. O lp pm (detection limit). In addition, 100 mg of this hydrogenated resin was burned in a Doman combustor, absorbed in 5 ml of pure water, and analyzed by ion chromatography. As a result, the chlorine atomic weight was 0.02 ppm (detection limit). It was below.

To 60 parts by weight of the hydrogenated resin, 0.03 parts by weight of an antioxidant (manufactured by Ciba Geigy Co., Ltd., Irganox 101) was added, and a twin-screw extruder (TEM-M, manufactured by Toshiba Machine Co.) Extruded at 35 B, screw diameter 35 mm, screw rotation speed 150 rpm, resin temperature 300, and pelletized. Was.

Using this pellet, injection molding (made by Toshiba Machine Co., Ltd., IS-350 FB-119 AP mold clamping pressure 350 ton, resin temperature 330 ° C, mold temperature 120 ° C) Then, a test plate having a diameter of 100 mm and a thickness of 1.2 mm and a cylindrical transparent container having a diameter of 200 mm, a height of 130 mm and an average thickness of 3 mm were prepared. The test plate was colorless and transparent, and the light transmittance of the test plate having a thickness of 1.2 mm was 90.4% and the birefringence value was 25 nm or less. The volume resistivity measured using the test plate state, and are 5 X 1 0 ¹⁶ Ω cm or more, any frequency of ^{1 0 2 H z, 1 0} 6 H z and 1 0 ⁹ H z in also the dielectric constant and dielectric loss tangent were respectively 2.3 6 with 5 X 1 0- ^4. This proved that this hydrogenated resin was suitable as an optical material and an electrical insulating material.

 [Example 16]

 2% by weight agar was added to the LB medium, and the mixture was steam-sterilized at 121 ° C for 30 minutes to form a gel. Before solidification, 300 ml of the container was molded in Example 15 After leaving it at room temperature for 6 hours, it was covered with aluminum foil, and steam sterilized at 121 ° C for 30 minutes. The appearance of the container after the treatment was good, and no turbidity, cracking or deformation was observed. After the treatment, the cells were incubated at 37 for 3 days, but no fungal growth was observed.

A 2 mm thick test plate formed in Example 15 was cut into a 10 mm width, used as a test piece, ultrasonically cleaned in distilled water for 20 minutes, and dried at 40 for 10 hours. The test piece was subjected to an elution test according to the Japanese Pharmacopoeia No. 12 Revised “Plastic Test Method for Infusion Solutions”. The bubbling disappeared within 3 minutes, the pH difference was -0.01, the ultraviolet absorption was 0.004, and the permanganate-reducing substance was 0.16 ml. This proved that this hydrogenated resin was suitable as medical equipment. [Example 17]

 The test specimen prepared in Example 16 was subjected to 70% nitric acid, phosphoric acid, hydrofluoric acid (hydrofluoric acid 7% by weight, nitric acid 42% by weight, water 51%), 37% hydrochloric acid, 30% diluted sulfuric acid , Concentrated sulfuric acid, 30% aqueous hydrogen peroxide, saturated aqueous solution of potassium hydroxide, 29% aqueous ammonia, acetate, isopropyl alcohol, trichloroethylene, 2.38% by weight tetramethylammonium The solution was immersed in an aqueous solution of oxide for oxide and an aluminum etchant (80% by weight of concentrated phosphoric acid, 5% by weight of nitric acid, 5% by weight of glacial acetic acid, and 10% of water) for 5 minutes. Although it swelled with ethylene at the trichloride and darkened the surface with concentrated sulfuric acid, it was not affected by other chemicals, indicating good chemical resistance.

200 g of this test piece was placed in a hard glass container, and 200 g of distilled water was added. And a hard glass cap, was immersed for 24 hours at 8 0, extracted organics were daily ^{2 X 1 0 2 g / m} z in total organic carbon content. After that, when the same test piece was immersed again in 200 g of distilled water at 80 ° C for 144 hours, the total amount of extracted organic carbon was 7 gZm ² or less, which is the measurement limit per day.

 From these results, it was found that this hydrogenated resin was suitable as a device for manufacturing electronic components.

 [Comparative Example 4]

 An attempt was made to pelletize the copolymer obtained in Reference Example 8 in the same manner as in Example 15, but the coloring and burnt were so severe that pelletization was not possible.

 [Comparative Example 5]

In a reactor purged with nitrogen, 300 parts by weight of toluene, 20 parts by weight of methylaluminoxane dissolved in 50 parts by weight of toluene, 15 parts by weight and nickel bisacetyl acetate toner 0.07 parts by weight Parts were added. Next Then, a solution composed of 470 parts by weight of norbornene and 200 parts by weight of toluene was added, and the mixture was reacted at 50 ° C. for 5 hours. After the addition of 10 parts by weight of methanol to terminate the reaction, the reaction mixture was poured into 300 parts by weight of methanol containing 5 parts by weight of concentrated hydrochloric acid for stirring to coagulate the polymer. After filtering and collecting the polymer, the polymer was washed with 500 parts by weight of methanol and dried at 100 ° C. and 1 torr or less for 48 hours to obtain 320 parts by weight of a norbornene addition polymerization type polymer. .

 The intrinsic viscosity of this polymer was 1.24 d 1, and the glass transition temperature was 300 ° C. or higher. The polymer was heated and heated to 400 ° C. in nitrogen, but decomposition started without melting, and it could not be melt-molded. Industrial applicability

 The hydrogenated resin of the present invention does not contain a crosslinked gelled material, and is excellent in transparency, low birefringence, light resistance, moisture resistance, moldability, electrical insulation, mechanical strength, etc. It is suitable for the fields of materials, medical polymer materials, electrical insulation materials, and electronic component materials.

Claims

The scope of the claims

1. A resin obtained by hydrogenating a polymer containing a linear addition polymerization type repeating unit of a cyclopentadiene monomer, wherein at least 90% of carbon-carbon double bonds in the repeating unit are contained. A hydrogenated resin which has been hydrogenated and has an intrinsic viscosity measured in toluene at 25 ["] 0.1 to 10 dl.

 2. The hydrogenated resin according to claim 1, wherein the polymer is a linear addition polymer type homopolymer of a cyclopentadiene monomer.

 3. The polymer is composed of at least 10% by weight of a linear addition polymer type repeating unit of a cyclopentadiene monomer and a repeating unit derived from a monomer copolymerizable with the cyclopentadiene monomer. The hydrogenated resin according to claim 1, which is a copolymer containing 90% by weight or less of a unit.

 4. Monomers copolymerizable with a cyclopentadiene monomer include a-olefin, conjugated diene, cyclic ether, vinyl ether, heterocyclic ring-containing vinyl compound, cyclic olefin, and vinyl group-containing cyclic hydrocarbon. 4. The hydrogenated resin according to claim 3, which is a monomer or a norbornene-based monomer.

 5. The polymer comprises 60% by weight or more of a linear addition-polymer type repeating unit of a cyclopentadiene monomer, and a vinyl compound containing a heterocyclic ring, a conjugated gen, a cyclic ether, a vinyl ether, or a heterocycle. Or a copolymer containing 40% by weight or less of a linear addition polymerization type repeating unit of a cyclic olefin, wherein at least 90% of carbon-carbon double bonds in the copolymer are contained. 5. The hydrogenated resin according to claim 4, wherein is hydrogenated.

6. The polymer has linear addition weight of cyclopentadiene monomer. It contains 10 to 90% by weight of a combined repeating unit and 90 to 10% by weight of a linear addition polymerization type repeating unit of a vinyl group-containing cyclic hydrocarbon monomer or a norbornene-based monomer. The hydrogenated resin according to claim 4, which is a copolymer, wherein at least 90% of carbon-carbon double bonds in the copolymer are hydrogenated.

 7. The polymer has a linear addition polymerization type repeating unit of a cyclopentadiene monomer of 10 to 50% by weight, and a linear addition polymerization type of a vinyl group-containing cyclic hydrocarbon monomer. 7. The hydrogenated resin according to claim 6, which is a copolymer containing 90 to 50% by weight of a repeating unit.

 8. The polymer is composed of 10 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and 90 to 50% by weight of a linear addition polymerization type repeating unit of a norbornene monomer. 7. The hydrogenated resin according to claim 6, which is a copolymer containing 50% by weight.

 9. The hydrogenated resin according to any one of the preceding claims, which is used as an optical material, a medical polymer material, an electrical insulating material, or an electronic component material.

 10 0 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and 90% by weight of a linear addition polymerization type repeating unit of a vinyl group-containing cyclic hydrocarbon monomer 90 A copolymer having an intrinsic viscosity [7?] Of 0.1 to LO LO dl Zg measured in toluene at 25 ° C.

 1 1. 10 to 50% by weight of a linear addition polymerization type repeating unit of a cyclopentadiene monomer and 90 to 50% by weight of a linear addition polymerization type repeating unit of a norbornene monomer % And a limiting viscosity [7?] Measured in toluene at 25 ° C. of 0.1 to 10 d 1 / g.