JP4678367B2 - Film made of cyclic olefin-based (co) polymer, film made of cyclic olefin-based (co) polymer composition, and crosslinked film of cyclic olefin-based (co) polymer - Google Patents

Description

  The present invention relates to a film comprising a cross-linkable cyclic olefin-based (co) polymer. More specifically, a film made of a crosslinkable cyclic olefin-based (co) polymer suitable for an optical material having excellent heat resistance, solvent resistance, and chemical resistance, a film made of the composition thereof, and a crosslinked film thereof About.

  Cyclic olefin polymers have excellent optical transparency, heat resistance, electrical insulation, low dielectric constant, low water absorption, and the like, and have been developed in various applications in recent years. For example, in the field of optical materials, conversion from a conventionally used glass to a transparent resin is progressing with demands for weight reduction, size reduction / densification, good workability, and prevention of cracking. However, transparent resin as an alternative to glass has the advantages of being easy to process, hard to break, and light, but has poor heat resistance, durability and chemical resistance, and dimensional stability, so these drawbacks should be improved. Is required.

Polymer cross-linking is cited as a powerful means to remedy these drawbacks. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 03-205408) discloses a cyclic olefin addition polymer represented by a vinyl group or a vinylidene group and having a hydrocarbon unsaturated bond in the side chain. Further, in Patent Document 2 (Japanese Patent Laid-Open No. 10-251343), a norbornene polymer having an alkenyl group, an alkylidene group, or an epoxy group is disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 10-182799). Norbornene-based polymers having groups are disclosed respectively. However, when an unsaturated bond group such as a vinyl group or a vinylidene group is used as a crosslinkable reaction site, the oxidation deterioration resistance is lowered, causing problems such as coloring at a high temperature. Further, in order to crosslink, a large amount of an initiator compound that decomposes with heat or light to generate radicals is required, but this leads to deterioration of the polymer. Epoxy groups are generally unstable.
Further, regarding cyclic olefin copolymers using a hydrolyzable silyl group as a crosslinking reaction site, Patent Document 4 (Japanese Patent Laid-Open No. 07-104474), Patent Document 5 (WO 98/56839), Patent Document 6 (WO97 / 20871), Patent Document 7 (WO98 / 20394), and the like. The polymer is crosslinked by hydrolysis followed by a condensation reaction, but this requires an equivalent amount of water molecules. For this reason, particularly a thick cyclic olefin polymer has a low water absorption rate, and it is necessary to carry out it under severe conditions in order to sufficiently advance the crosslinking reaction. Furthermore, hydrolyzable silyl groups generally have a problem in storage stability, such as being gradually hydrolyzed in a solution or the like to form a gel-like condensate. That is, there is a need for a cyclic olefin-based resin that is more excellent in chemical resistance, heat resistance, storage stability, and cross-linking curability while maintaining high optical transparency, but conventional techniques are insufficient.
Japanese Patent Laid-Open No. 03-205408 Japanese Patent Laid-Open No. 10-251343 JP-A-10-182799 Japanese Patent Laid-Open No. 07-104474 WO98 / 56839 WO97 / 20871 Publication WO98 / 20394

  The present invention has been made in view of the above-mentioned problems, and can maintain a high optical transparency, storage stability, and heat resistance while providing excellent chemical resistance and solvent resistance. It is an object of the present invention to provide a film comprising a co) polymer, a film comprising the composition, and a crosslinked film thereof.

The present invention relates to a film comprising a cyclic olefin-based (co) polymer containing at least one structural unit of a cyclic olefin having an oxetane skeleton and having a polystyrene-equivalent number average molecular weight of 5,000 to 1,500,000. About.
The present invention also relates to a film comprising the above cyclic olefin (co) polymer and a cyclic olefin (co) polymer composition comprising an oxetanyl group ring-opening reaction initiator.
Furthermore, this invention relates to the crosslinked body film of a cyclic olefin (co) polymer formed by bridge | crosslinking the film which consists of said cyclic olefin type | system | group (co) polymer composition.

  According to the present invention, from a crosslinkable cyclic olefin-based (co) polymer capable of imparting excellent chemical resistance and solvent resistance while maintaining high optical transparency, storage stability, and heat resistance. The film which consists of, the film which consists of the composition, and also the crosslinked body film can be provided.

  As a result of intensive studies by the present inventors, a cyclic olefin-based (co) polymer containing at least one structural unit of a cyclic olefin having an oxetane skeleton, and ring opening of the cyclic olefin-based (co) polymer and an oxetanyl group By using the composition with the reaction initiator, it becomes clear that a film capable of imparting excellent chemical resistance and solvent resistance can be obtained while maintaining the high optical properties of the cyclic olefin, and the present invention is completed. It came to. In particular, it has been found that a film comprising a composition comprising the cyclic olefin-based (co) polymer and a photoacid generator is a film having excellent photocrosslinkability.

  The oxetane skeleton is a unit capable of cationic polymerization, and in particular, a photopolymerization system of an oxetane compound using a photocationic polymerization initiator can be polymerized at room temperature and exhibits high productivity. In addition, it is known that it is less susceptible to oxygen inhibition during the polymerization reaction than an acrylate polymerization system. There is an epoxy compound having the same photocationic polymerizability, but its polymerizability is low, and furthermore, it is generally unstable, so there is a problem in stability during production process and long-term storage. On the other hand, the oxetane compound is very stable in the absence of an acid and has a feature of having high cationic polymerizability as compared with an epoxy compound. Therefore, the structural unit of the cyclic olefin having an oxetane skeleton has high stability, and at the same time, the crosslinking proceeds promptly with a small amount, so that it is excellent as a crosslinking reaction site of the cyclic olefin-based (co) polymer. It is.

  In addition, the cyclic olefin-based (co) polymer of the present invention has excellent characteristics when compared with crosslinking with a hydrolyzable silyl group. Hydrolyzable silyl groups such as alkoxysilyl groups require an equivalent amount of water for the crosslinking reaction, and therefore more severe conditions are required. If it remains in the crosslinked body, it may cause a decrease in transmittance due to light scattering. On the other hand, the oxetanyl group does not have such a problem in the crosslinking reaction, and can be crosslinked while maintaining high optical transparency under mild conditions. Furthermore, the hydrolyzable silyl group may be gradually hydrolyzed by moisture to cause gelation.

  The cyclic olefin-based (co) polymer having an oxetane skeleton of the present invention desirably has at least a structural unit derived from a cyclic olefin having an oxetanyl group represented by any of the following formulas (1) to (4). One type of cyclic olefin addition (co) polymer or ring-opening (co) polymer hydride.

[In the formulas (1) to (4), A ¹ , A ² and A ³ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group or a cycloalkyl group. is ^{(CR 6} R ₇₎ group selected from a polar group represented by _q Z - group, an aryl group or. Here, Z represents —OR ⁸ , —C (O) R ⁹ , —OC (O) R ¹⁰ , C (O) OR ¹¹ or —SiY ¹ Y ² Y ³ , and Y ^{1 to} Y ³ are the same or Differently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, an allyloxy group, a siloxy group, or a polyvalent one that forms a 5- to 8-membered ring by bonding to each other Represents an alcohol residue. X is a group which connects the cyclic olefin and an oxetanyl _{^{group, - (CR 12 R 13)}} r -, or _{^{- (CR 14 R 15) s}} -T- (CR 16 R 17) t - represents, T Represents —O—, —C (O) —, —OC (O) —, C (O) O—, —SiR ¹⁸ R ¹⁹ —. R ^{1 to} R ¹⁹ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, p and q are integers of 0 to 3, and r, s and t are 0 to 6 Represents an integer. ]

  The cyclic olefin-based (co) polymer of the present invention can be obtained, for example, by polymerizing a cyclic olefin having an oxetanyl group as a monomer. For example, the structural units represented by the formulas (1) and (2) are formed by addition polymerization of a cyclic olefin having an oxetanyl group represented by the following formulas (7) and (8), respectively. On the other hand, the structural units represented by the formulas (3) and (4) are formed by subjecting the cyclic olefins represented by the following formulas (7) and (8) to ring-opening polymerization and hydrogenation, respectively.

[In the formulas (7) and (8), A ¹ , A ² , A ³ , R ^{1 to} R ⁵ , p are the same as those in the formulas (1) to (4). ]

Examples of the cyclic olefin represented by the formula (7) include 5- (3-oxetanyl) bicyclo [2.2.1] hept-2-ene, 5- (3-methyl-3-oxetanyl) bicyclo [2]. 2.1] hept-2-ene, 5- (3-ethyl-3-oxetanyl) bicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methyl] bicyclo [2. 2.1] Hept-2-ene, 5-[(3-methyl-3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) Methyl] bicyclo [2.2.1] hept-2-ene and other oxetanyl groups bonded to a cyclic olefin via a carbon chain, 2-[(3-oxetanyl) methoxy] bicyclo [2.2.1] Hept-5-ene, 2-[(3- Ru-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, 5-[(3-Oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept- 2-ene, 5-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methoxyethyl] bicyclo [2.2. 1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methoxyethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methoxy Ethyl] Bishi B [2.2.1] hept-2-ene, 8 - [(3-oxetanyl) methoxy] tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8-[(3-methyl-3-oxetanyl) methoxy] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-ethyl-3-oxetanyl) methoxy] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-methyl-3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-ethyl-3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-[(3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, 5,6-bis [(3- Oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5,6-bis [(3-methyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene , 5,6-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, and the like linked by an ether bond,
5-[(3-Oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept- 2-ene, 5-[(3-ethyl-3-oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methylcarbonylmethyl] bicyclo [2.2 .1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methylcarbonylmethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) ) Methylcarbonylmethyl] bicyclo [2.2.1] hept-2-ene and the like bonded by a carbonyl group,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-methyl-3- Oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl, 2-methylbicyclo [2.2.1] hept-5-ene- 2-Carboxylic acid (3-oxetanyl) methyl, 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-methyl-3-oxetanyl) methyl, 2-methylbicyclo [2. 2.1] Hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-oxetanyl) methoxymethyl], tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-methyl-3-oxetanyl) methoxymethyl], tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-ethyl-3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-methyl-3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-ethyl-3-oxetanyl) methoxymethyl], bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (3 -Oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (3-methyl-3-oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene- 1,3-dicarboxylic acid (3-ethyl-3-oxetanyl) methyl, and the like bonded by an ester bond,
5- (3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5- (3-methyl-3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5- (3-ethyl-3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] hept-2 -Ene, 5-[(3-methyl-3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] Those bonded by a silyl group such as hept-2-ene are preferably used, but are not limited thereto.

Examples of the cyclic olefin represented by the formula (8) include spiro-oxetane-5,3′-bicyclo [2.2.1] hept-2-ene, spiro-oxetane-8,3′-tetracyclo. [4.4.0.1 ^2,5 . Cyclic olefins in which an oxetane ring is bonded by a spiro structure, such as ^{17, 10} ] dodec-3-ene, are desirably used.

  In addition, the structural units represented by the formulas (1) to (4) are not a method of polymerizing the cyclic olefin having the oxetanyl group shown above, but the precursor compound is polymerized in advance and then subjected to some treatment. May be generated. For example, by polymerizing a cyclic olefin having a 6-membered cyclic ester carbonate as a substituent as a monomer, and heating / decarboxylating the resulting cyclic olefin-based (co) polymer, the oxetane in the polymer A skeleton may be generated.

  The structural units represented by the above formulas (1) to (4) may be only one type, or two or more types may coexist. In the cyclic olefin-based (co) polymer of the present invention, the ratio of these structural units is preferably 0.01% or more, more preferably 0.1% or more, and most preferably 0.1% in terms of a molar ratio to all units. To 30%. When this ratio is less than 0.01%, the effect of crosslinking is hardly obtained.

  In addition to the structural unit derived from the cyclic olefin having an oxetane skeleton, the cyclic olefin-based (co) polymer of the present invention may optionally contain a structural unit represented by any of the following formulas (5) or (6). Good.

[In the formulas (5) and (6), B ¹ , B ² , B ³ and B ⁴ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group, A cycloalkyl group, an aryl group, a polar group represented by — (CR ²⁰ R ²¹ ) _v Z, an alkylidene group formed by B ¹ and B ² , an alkylene group in which B ¹ and B ³ are bonded, a cycloalkylene group, It is a group selected from an alkenylene group, a cycloalkenylene group and an arylene group, and B ¹ and B ² or B ¹ and B ³ may be ring-closed to form a lactone or an acid anhydride. R ²⁰ and R ²¹ are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and Z is the same as in formulas (1) to (4). u and v represent an integer of 0 to 3. ]

  The structural units represented by the above formulas (5) and (6) are formed by copolymerizing a cyclic olefin represented by the following formula (9).

[In the formula (9), B ¹ , B ² , B ³ , B ⁴ and u are the same as those in the formulas (5) and (6). ]

Specific examples of the cyclic olefin represented by the formula (9) include bicyclo [2.2.1] hept-2-ene (norbornene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-propylbicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene 5-pentylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-heptylbicyclo [2.2.1] hept-2- Ene, 5-octylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, 5-dodecylbicyclo [2.2.1] hept-2 -Ene, 5,5-dimethylbicyclo [2.2.1] hept-2 Ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethylbicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2 .1] Hept-2-ene, 5-allylbicyclo [2.2.1] hept-2-ene, 5-methylenebicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2. 2.1] Hept-2-ene, 5-isopropylidenebicyclo [2.2.1] hept-2-ene, 5-cyclohexylbicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenylbicyclo [2.2.1] hept-2-ene, 5-phenylmethylbicyclo [2.2.1] hept-2-ene, 1, 4-methano-1,4-dihydronaphthalene Zonorbornene), 5-fluorobicyclo [2.2.1] hept-2-ene, 5-chlorobicyclo [2.2.1] hept-2-ene, 5-bromobicyclo [2.2.1] hept 2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-chloromethylbicyclo [2.2.1] hept-2-ene, 5- (1-chloroethyl) bicyclo [ 2.2.1] Hept-2-ene, 5- (2-chloroethyl) bicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2- Ene, 5-trifluoromethyl-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene, 5-pentafluoroethylbicyclo [2.2.1] hept-2-ene, 5 -Pentafluoroethyl-5,6,6-to Rifluorobicyclo [2.2.1] hept-2-ene, 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-chlorodimethoxysilylbicyclo [2.2.1] hept- 2-ene, 5-dichloromethoxysilylbicyclo [2.2.1] hept-2-ene, 5-chloromethoxymethylsilylbicyclo [2.2.1] hept-2-ene, 5-methoxydimethylsilylbicyclo [ 2.2.1] Hept-2-ene, 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 5-chlorodiethoxysilylbicyclo [2.2.1] hept-2-ene 5-dichloroethoxysilylbicyclo [2.2.1] hept-2-ene, 5-chloroethoxymethylsilylbicyclo [2.2.1] hept-2-ene, 5-ethoxydimethylsilane Rubicyclo [2.2.1] hept-2-ene, 5-tripropoxysilylbicyclo [2.2.1] hept-2-ene, 5-triisopropoxysilylbicyclo [2.2.1] hept-2 -Ene, 5-triphenoxysilylbicyclo [2.2.1] hept-2-ene, 5-diphenoxymethylsilylbicyclo [2.2.1] hept-2-ene, 5-trifluorosilylbicyclo [2 2.1] hept-2-ene, 5-trichlorosilylbicyclo [2.2.1] hept-2-ene, 5- (1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl) ) Bicyclo [2.2.1] hept-2-ene, 5- (1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl) bicyclo [2.2.1] hept-2-ene , 5- (1 ′, 4 ′, 4′-trimethyl- 2 ′, 6′-dioxa-1′-silacyclohexyl) bicyclo [2.2.1] hept-2-ene, 5-trimethoxysilylmethylbicyclo [2.2.1] hept-2-ene, 5- (1-trimethoxysilylethyl) bicyclo [2.2.1] hept-2-ene, 5- (2-trimethoxysilylethyl) bicyclo [2.2.1] hept-2-ene, 5-triethoxy Silylmethylbicyclo [2.2.1] hept-2-ene, 5- (1-triethoxysilylethyl) bicyclo [2.2.1] hept-2-ene, 5- (2-triethoxysilylethyl) Bicyclo [2.2.1] hept-2-ene, 2-acetylbicyclo [2.2.1] hept-5-ene, methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate , Bicyclo [2.2.1] hept Ethyl 5-ene-2-carboxylate, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid-t-butyl, 2-methylbicyclo [2.2.1] hept-5-ene- Methyl 2-carboxylate, ethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid -T-butyl, 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid trifluoromethyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid trimethoxy Silylpropyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid triethoxysilylpropyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid dimethoxymethylsilylpropyl, 2 -Methyl Cyclo [2.2.1] hept-5-ene-2-carboxylic acid trimethoxysilylpropyl, 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid dimethoxymethylsilylpropyl, 2 -Methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid triethoxysilylpropyl, acetic acid bicyclo [2.2.1] hept-5-en-2-yl, acetic acid 2-methylbicyclo [ 2.2.1] Hept-5-en-2-yl, 2-methylbicycloacrylate [2.2.1] hept-5-en-2-yl, 2-methylbicyclomethacrylate [2.2. 1] Hept-5-en-2-yl, bicyclo [2.2.1] hept-5-en-2-ylmethyl acetate, bicyclo [2.2.1] hept-5-en-2-ylmethyl acrylate , Methacrylic acid Bicyclo [2.2.1] hept-5-en-2-ylmethyl, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, bicyclo [2.2.1] hept- Diethyl 5-ene-2,3-dicarboxylate, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, tricyclo [4.3.0.1 ^{2, 5]} deca-3,7-diene And those derived from (dicyclopentadiene) and spiro ring compounds as shown below.

These can be used alone or in combination of two or more.
In the cyclic olefin-based (co) polymer of the present invention, the proportion of the structural unit represented by the formula (5) or (6) is preferably 0 to 99.99%, more preferably 0, in terms of a molar ratio to the total units. To 99.9%, most preferably 70 to 99.9%.

  For example, in addition to the structural unit of the cyclic olefin having an oxetane skeleton, the glass transition temperature of the obtained (co) polymer is controlled by arbitrarily including the structural unit of an alkyl-substituted cyclic olefin having 3 to 10 carbon atoms. Workability can be improved, and flexibility can be imparted to the resulting molded article. Furthermore, what contains the structural unit of the cyclic olefin which has a moderate ratio of alkoxy silyl groups can be used suitably for a composite with metal oxides, such as a silica, an alumina, a titania, a zirconia.

  The cyclic olefin-based (co) polymer of the present invention is optionally further monocyclic olefins such as bicyclo [2.2.1] hept-3,5-diene (norbornadiene), one or more kinds of cyclobutene, cyclopentene, and cyclohexene. Structural units derived from can be included.

  When the cyclic olefin-based (co) polymer of the present invention is an addition polymer, it may further optionally contain one or more structural units represented by the following formula (10). The structural unit represented by the formula (10) can be formed by addition copolymerization of an α-olefin or an aromatic vinyl compound represented by the general formula (11).

—CH ₂ —CH (R ²² ) — (10)
[In the formula (10), R ²² represents a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, and an alkoxysilyl group. is there. ]

CH ₂ = CH (R ²² ) (11)
[In formula (11), R ²² is the same as formula (10)]

  Specific examples of these α-olefins and aromatic vinyl compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 7-methyl-1,6-octadiene, Examples include vinyltrimethylsilane, vinyltriethylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, trichlorovinylsilane, styrene, 2-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, vinylnaphthalene, and the like.

  In the cyclic olefin-based (co) polymer of the present invention, a structural unit derived from the above bicyclo [2.2.1] hept-3,5-diene or a monocyclic olefin, and a structural unit represented by the formula (10) Are used in the range of 0 to 50%, preferably 0 to 30%, respectively, in molar ratio to the total units. If this ratio exceeds 50%, the glass transition temperature of the cyclic olefin-based (co) polymer of the present invention will be low, and the heat resistance will be impaired.

  For the production of the cyclic olefin-based (co) polymer of the present invention, the following method is preferably used.

When the cyclic olefin-based (co) polymer is an addition (co) polymer containing a structural unit represented by either the above formula (1) or (2), the polymerization catalyst may be (A) Those containing transition metal compound components are used, preferably those containing group 8-10 transition metal compound components of the periodic table, more preferably selected from the group of nickel, cobalt and palladium compounds listed below. Is used.
β-diketonate compounds;
Nickel bisacetylacetonate, nickel bisacetoacetate ethyl, cobalt bisacetylacetonate, palladium bisacetylacetonate, etc. carboxylate;
Nickel acetate, nickel propionate, nickel 2-ethylhexanoate (nickel octylate), nickel 3,5,5-trimethylhexanoate (nickel isononanoate), nickel octoate, nickel naphthenate, nickel neodecanoate, cyclohexylcarboxylic acid Nickel, nickel laurate, nickel stearate are mentioned, and nickel bisacetylacetonate, nickel 2-ethylhexanoate, nickel 3,5,5-trimethylhexanoate, nickel octoate, nickel naphthenate, neodecane are particularly desirable. Nickel oxide, nickel cyclohexylcarboxylate, nickel laurate, nickel stearate, cobalt acetate, cobalt propionate, cobalt 2-ethylhexanoate, cobalt naphthenate, cobalt decanoate , Cobalt laurate, cobalt stearate, palladium acetate, palladium propionate, 2-ethylhexanoic acid palladium, naphthenic acid palladium, etc. neodecanoate palladium.
A strong Bronsted acid-modified compound such as tetrafluoroboric acid, hexafluorophosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, hexafluoroantimonic acid or the like of the β-diketonate compound or the carboxylate.
A compound having a transition metal-carbon bond, or η ³ -allyl, η ⁶ -arene, diene, triene complex compound;
Di-μ-chlorobis (η ³ -allyl palladium), [(η ³ -crotyl) (1,5-cyclooctadiene) nickel] hexafluorophosphate, (methyl) (1,5-cyclooctadiene) palladium chloride , [(Η ³ -crotyl) (1,5-cyclooctadiene) palladium] hexafluorophosphate, (η ⁶ -benzene) bis (pentafluorophenyl) nickel, (η ⁶ -toluene) bis (pentafluorophenyl) Nickel, (η ⁶ -benzene) bis (trichlorosilyl) nickel, (η ⁶ -toluene) bis (trichlorosilyl) nickel, [6-methoxynorbornen-2-yl-5-palladium (cyclooctadiene)] hexafluorophosphate Such.
A transition metal complex compound having a ligand having a hetero atom such as P, N, or O;
[Tetrakis (acetonitrile) palladium] tetrafluoroborate, tetrakis (benzonitrile) palladium, bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine) cobalt dibromide, bis (tri Phenylphosphine) palladium dichloride, [1,2-bis (diphenylphosphino) ethane] nickel dichloride, [1,2-bis (diphenylphosphino) ethane] nickel dibromide, [1,2-bis (diphenylphosphino) Ethane] cobalt dibromide, [1,2-bis (diphenylphosphino) ethane] palladium dichloride, [1,2-bis (diphenylphosphino) ethane] palladium methyl chloride, Methyl phosphine imide nickel bromide tetramer, bis [N- (3-tert- butylsalicylidene) phenyl aminate] nickel or,

Palladium diimine complexes such as these, or complexes in which these metal species are replaced with nickel or cobalt,

[In the above compounds, Ph represents a phenyl group, and Cy represents a cyclohexyl group. ]
(P-O chelate) nickel complexes.
Said (A) transition metal compound component can be used alone or in combination of two or more. Moreover, these (A) transition metal compound components may be used as a single component catalyst, or combined with components selected as necessary from the promoter components shown in the following (B) to (E). Alternatively, it may be used as a multi-component catalyst system.

Co-catalyst components to be combined when used as a multi-component catalyst system include (B) organoaluminums such as trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, alkylaluminum sesquihalide, alkylaluminoxane; boron trifluoride diethyl ether (C) Lewis acid compounds such as complexes, tris (pentafluorophenyl) boron, aluminum trifluoride, titanium tetrachloride, antimony pentafluoride; tetrafluoroboric acid, hexafluorophosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid (D) strong Bronsted acids such as hexafluoroantimonic acid;
[L] ⁺ [An] ⁻
(E) ionic compound represented by (wherein [L] ⁺ represents a Lewis acid, Bronsted acid, ammonium, or a cation of a metal atom, and [An] ⁻ represents a non-coordinating anion. .).

  Examples of the ionic compound (E) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, dimethylanilinium tetraphenylborate, and methyl tetraphenylborate. Pyridinium, triphenylmethyl tetraphenylborate, ferrocenium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, tetrakis (Pentafluorophenyl) methyldibutylammonium borate, tetrakis (pentafluorophenyl) borate dimethylanilinium , Tetrakis (pentafluorophenyl) methylpyridinium borate, trikismethyl tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis [3,5- Di (trifluoromethyl) phenyl] dimethylanilinium borate, tetrakis [3,5-di (trifluoromethyl) phenyl] triphenylmethyl borate, tetrakis [3,5-di (trifluoromethyl) phenyl] boric acid Examples thereof include, but are not limited to, sodium, silver tetraphenylborate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroantimonate and thallium hexafluorophosphate.

Examples of (A) used as a single component catalyst containing only a transition metal compound component include (η ⁶ -benzene) bis (pentafluorophenyl) nickel, (η ⁶ -toluene) bis (pentafluorophenyl) nickel, (η ⁶ -Mesitylene) bis (pentafluorophenyl) nickel and the like.

Examples of the multi-component catalyst system used in combination of (A) transition metal compound component and (B) organoaluminum include nickel 2-ethylhexanoate and methylaluminoxane (hereinafter abbreviated as “MAO”), Trimethylphosphine imide nickel bromide tetramer and MAO, (η ⁶ -benzene) bis (trichlorosilyl) nickel and ethylaluminum dichloride, (η ⁶ -toluene) bis (trichlorosilyl) nickel and ethylaluminum dichloride, di-μ-chlorobis (6-methoxynorbornen-2-yl-5-palladium) and MAO, cobalt neodecanoate and MAO.

Examples of the multi-component catalyst system used in combination of the (A) transition metal compound component and the (E) ionic compound include di-μ-chlorobis (η ³ -allyl palladium) and silver hexafluoroantimonate. , Di-μ-chlorobis (6-methoxynorbornen-2-yl-5-palladium) and silver hexafluoroantimonate, a mixture of (methyl) (1,5-cyclooctadiene) palladium chloride and triphenylphosphine and tetrakis [3,5-di (trifluoromethyl) phenyl] sodium borate and the like.

  Examples of the multi-component catalyst system used in combination of the above (A) transition metal compound component, (B) organoaluminum, and (C) Lewis acid compound include hexafluoroantimonic acid nickel 2-ethylhexanoate. Examples of the modified compound include triethylaluminum and boron trifluoride diethyl ether complex, hexafluoroantimonic acid modified compound of nickel 2-ethylhexanoate, MAO and boron trifluoride diethyl ether complex, and the like.

  Examples of the multi-component catalyst system used in combination of the (A) transition metal compound component, (B) organoaluminum, and (E) ionic compound include nickel 2-ethylhexanoate, triethylaluminum, and tetrakis. Combinations of triphenylmethyl (pentafluorophenyl) borate, nickel 2-ethylhexanoate, triethylaluminum, dimethylanilinium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

  The transition metal compound component (A) and the promoter component (B) to (E) may be independently introduced into a container for performing a polymerization reaction, or two or more components may be mixed in advance.

When the cyclic olefin-based (co) polymer is a hydride of a ring-opening (co) polymer containing a structural unit represented by either the above formula (3) or (4), A known catalyst may be used as the polymerization catalyst. For example, a single component catalyst or a multicomponent catalyst as shown below can be used. As the single component catalyst, biscyclopentadienyl-3,3-dimethyl titanacyclobutane, biscyclopentadienyl-3-t-butyl titanacyclobutane,
W (OR ²³ ) ₂ (= NAr) (= CH (C (CH ₃ ) ₂ R ²⁴ ),
Mo (OR ²⁵ ) ₂ (= NAr) (= CH (C (CH ₃ ) ₂ R ²⁶ ),
W (Br) ₂ (OCH ₂ (t-Bu)) ₂ (= CH (t-Bu)),
W (CO) ₄ (= C (OMe) (CH ₂ CH ₂ CH═CH ₂ ),
RuCl ₂ [PPh ₃ ] ₂ (= CHCO ₂ Et),
RuCl ₂ [PCy ₃ ] ₂ (= CHCH = CPh ₂ ),
RuCl ₂ [PCy ₃ ] ₂ (= CHPh),
Ta (OAr) ₃ (= CH (t-Bu)),
Ta (SAr ′) ₃ (= CH (t-Bu))
[Wherein R ^{23 to} R ²⁶ represent a hydrocarbon group or a halogenated hydrocarbon group, and Ar and Ar ′ each represent an aromatic substituent. And the like.

  The multi-component catalyst includes (F) at least one selected from compounds of tungsten, molybdenum, rhenium, titanium, and hafnium, and (G) a periodic table IA, IIA, IIB, IIIA, IVA, or IVB group element. (H) is preferably used in combination with at least one selected from compounds having a metal-carbon bond or metal-hydrogen bond, and if necessary, the catalytic activity is improved An agent (activity improver) may be further combined. As the component (F), tungsten, molybdenum, rhenium, titanium, hafnium halide, oxyhalide, alkoxide, phenoxide, carboxylate, β-diketonate compound, sulfonate, phosphate, phosphite, Carbonyl complexes, acetonitrile complexes, cyclopentadienyl complexes, indenyl complexes, hydride complexes, and derivatives thereof are preferably used, and tungsten and molybdenum compounds, particularly alkoxides, phenoxides, halides, and oxyhalides, have high polymerization activity. Is preferable.

Specific examples include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WBr ₄ , WOCl ₄ , WOBr ₄ , W (OC ₆ H ₅ ) ₆ , WCl ₄ (OCH ₂ CH ₂ Cl) ₂ , WCl _2. (OC ₆ H ₅ ) ₄ , WOCl ₂ [OC ₆ H ₃ -2,6- (i-Pr) ₂ ] ₂ , WO (OC ₆ H ₃ -2,6-Me ₂ ) ₄ , MoCl ₅ , MoCl ₃ , Mo (OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , Mo (CO) ₅ (C ₅ H ₅ N), WCl ₆ · (C ₅ H ₅ N), ReOCl ₃ , Re (CO) ₅ Cl _{, TiCl 4, HfCl 4, ZrCl} 4, (η 5 -C 5 H 5) 2 TiCl 2, and the like ^{_{(η 5 -C 9 H 7)}} 2 TiCl 2. These can be used alone or in combination of two or more.

  Examples of the component (G) include organic lithiums such as methyl lithium, ethyl lithium, butyl lithium, phenyl lithium and cyclopentadienyl lithium, organic sodium such as cyclopentadienyl sodium, dimethyl magnesium, diethyl magnesium and dibutyl. Organomagnesiums such as magnesium, ethylmagnesium halide, butylmagnesium halide, trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum hydride, organoaluminum such as alkylaluminoxane, dialkylzinc Organic zinc such as tetraalkyltin, organic tin such as tetraphenyltin, lithium hydride, lithium hydride Arm aluminum, sodium hydride, sodium borohydride, and metal hydrides such as aluminum hydride can be used.

  The component (G) is preferably used in a range of 1 to 100 times, more preferably 2 to 30 times in terms of a molar ratio converted to a metal atom with respect to the (F) component.

  (H) The activity improver is used as necessary to further improve the activity of ring-opening polymerization. Specific examples thereof include water, oxygen, acetaldehyde, acetaldehyde diethyl acetal, ethylene oxide, epichlorohydrin, N-nitrosodimethylaniline. , Tetrabutylammonium chloride, N-nitrosodiphenylamine, aluminum tribromide and the like. There are no particular restrictions on the amount added, and the optimum amount varies depending on the choice of (H) activity improver and other conditions, but it is used in a molar ratio of 0.005 to 10 times the component (F). Preferably, it is used in the range of 0.01 to 2 times.

  Next, in the hydrogenation reaction for obtaining a hydride of a ring-opening (co) polymer, the polymerized cyclic olefin-based ring-opening (co) polymer may be used as it is in the hydrogenation reaction, or the above catalyst. Alternatively, a (co) polymer having no residual monomer may be dissolved in a solvent and used in the hydrogenation reaction. The hydrogenation reaction is usually in the range of a hydrogen pressure of 1.0 to 10 MPa and the temperature of 50 to 200 ° C., and the hydrogenation catalyst is 10 to 1,000 ppm in terms of transition metal atoms with respect to the (co) polymer. Done in a range.

  As a hydrogenation catalyst, a metal selected from palladium, platinum, platinum, rhodium, iridium, ruthenium, nickel on a carrier selected from heterogeneous silica, alumina, zeolite, diatomaceous earth, magnesia, carbon, calcium carbonate, etc. , Or octenoate nickel / triethylaluminum, nickel naphthenate / triethylaluminum, cobalt octoate / triethylaluminum, cobalt octoate / n-butyllithium, biscyclopentadienyltitanium dichloride / diethylaluminum Chloride, palladium acetate / triethylaluminum, tris (triphenylphosphine) chlororhodium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, carbonyl Chlorohydridotris (tritolylphosphine) ruthenium, carbonylchlorohydridotris (trixylphosphine) ruthenium, carbonylchlorohydridotris (tricyclohexylphosphine) ruthenium, carbonyldihydridotris (triphenylphosphine) ruthenium, dichlorobis (triphenylphosphine) ruthenium A homogeneous catalyst such as is preferably used.

  The hydrogenated (co) polymer has better thermal stability as the hydrogenation rate is higher, that is, as the number of unreacted unsaturated bonds is smaller. As a result, it is possible to prevent thermal degradation due to heating, degradation due to oxygen, and the like in the subsequent solvent removal process and product molding process. The hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99% or more. When the hydrogenation rate of the (co) polymer is less than 90%, the heat deterioration resistance is insufficient.

  The molecular weight of the cyclic olefin-based (co) polymer of the present invention has a polystyrene-equivalent number average molecular weight of 5,000 to 1,500,000 as measured by gel permeation chromatography using o-dichlorobenzene as a solvent. Preferably it is 10,000-1,000,000. When the number average molecular weight is less than 5,000, the breaking strength when formed into a film, thin film, sheet or the like is insufficient, or the solvent resistance and liquid crystal resistance are inferior. On the other hand, when the number average molecular weight exceeds 1,500,000, the processability of the sheet and the film is lowered, or the solution viscosity becomes high at the time of forming the cast film, and the handling becomes difficult. The molecular weight of the cyclic olefin-based (co) polymer can be controlled by adding molecular weight regulators such as α-olefin compounds, aromatic vinyl compounds, cyclic non-conjugated polyenes, and hydrogen, and the amount of polymerization catalyst, as necessary. An appropriate method can be appropriately selected from a control method by adjusting the polymerization temperature, a control method by adjusting the conversion to (co) polymer, or a combination of these methods.

  Solvents for the polymerization reaction include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane, and aromatic hydrocarbons such as toluene, benzene and xylene. Solvent, halogenated hydrocarbon solvent such as dichloromethane, 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol, dimethyl ether, nitromethane, N-methylpyrrolidone, pyridine, N, A solvent selected from polar solvents such as N′-dimethylimidazolidinone, dimethylformamide, and acetamide is used.

  As a polymerization reaction method, in a nitrogen or argon atmosphere, a monomer composed of a solvent and a cyclic olefin is charged into a reaction vessel, a molecular weight regulator is added if necessary, the polymerization catalyst is added, and a temperature of -20 ° C to 100 ° C is added. Polymerization is carried out in the range of ° C. These polymerization operations can be carried out either batchwise or continuously.

  The polymerization is stopped by adding a compound selected from water, alcohol, organic acid, carbon dioxide, aldehyde and the like. If necessary, the polymerization catalyst residue from the polymerization reaction mixture may be separated and removed, and a known method may be appropriately used. For example, the polymerization reaction mixture may be washed with water or an alcohol solution by adding an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as maleic acid or fumaric acid. Further, the catalyst residue can be removed by adsorption using an adsorbent such as diatomaceous earth, alumina, silica, activated carbon, or a filtration operation using a filter. The cyclic olefin-based (co) polymer is obtained, for example, by putting the polymerization reaction mixture in an alcohol such as methanol, ethanol, isopropanol, solidifying, and drying under reduced pressure. By this step, the remaining unreacted monomer is also removed.

In the nuclear magnetic resonance spectrum of the cyclic olefin-based (co) polymer of the present invention, it is derived from a hydrogen nucleus bonded to a carbon atom adjacent to the oxygen of the oxetane ring within a chemical shift range of 4.2 ppm to 4.6 ppm. A characteristic absorption is observed. In the infrared absorption spectrum, for example, in a cyclic olefin-based (co) polymer containing 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, Strong absorption derived from the oxetane skeleton is observed around 985 cm ⁻¹ . That is, from these absorptions, the presence of the oxetane skeleton in the (co) polymer can be confirmed, and the structural unit containing it can be quantified.

  The cyclic olefin-based (co) polymer produced by the method of the present invention includes 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3- Methylphenol), 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythrityl Phenols such as tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, hydroquinone antioxidants, tris (4-methoxy-3,5-diphenyl) phosphite, tris ( Phosphorous antioxidants such as nonylphenyl) phosphite can be added to improve oxidation stability. When these antioxidants are added, they are preferably added in an amount of 0.05 to 5.0 parts by weight per 100 parts by weight of the cyclic olefin-based (co) polymer.

  Next, the cyclic olefin type (co) polymer composition of the present invention will be described. The cyclic olefin (co) polymer composition of the present invention comprises the cyclic olefin (co) polymer of the present invention and an oxetanyl group ring-opening reaction initiator. As the oxetanyl group ring-opening reaction initiator used, a compound that decomposes or cleaves by heating or the action of active energy rays to generate a strong acid, that is, a compound selected from a thermal acid generator or a photoacid generator, At least one kind is used. Known thermal acid generators and photoacid generators can be used. Typical examples include onium salts such as sulfonium salts, phosphonium salts, ammonium salts, and iodonium salts, diazomethane compounds, and aluminum complexes. Among them, the (co) polymer composition containing a photoacid generator can simplify the process such as being crosslinkable at room temperature in the crosslinking process, and has high productivity. Particularly desirable. These oxetanyl group ring-opening reaction initiators are used in the range of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the cyclic olefin-based (co) polymer. When the amount is less than 0.1 parts by weight, the crosslinking reaction does not proceed sufficiently, so that the required chemical resistance and solvent resistance cannot be obtained. On the other hand, when the amount exceeds 20 parts by weight, the resulting crosslinked product is obtained. Properties such as toughness, electrical properties, and hygroscopicity are reduced.

  Specific examples of the photoacid generator include onium salts such as unsubstituted or substituted diaryl iodonium, triarylsulfonium hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, and fluoroalkylsulfonate. Examples of the diazomethane compounds include, but are not limited to, unsubstituted or substituted α, α-bis (sulfonyl) diazomethane, α-carbonyl-α-sulfonyldiazomethane, and the like. It is not something.

  The cyclic olefin-based (co) polymer composition of the present invention may contain a photosensitizer in combination with a photoacid generator, if necessary. Here, the function of the photosensitizer is to absorb active energy rays and improve the sensitivity of the photoacid generator. Examples of the photosensitizer include benzoquinone, naphthoquinones, anthraquinones, thioxanthones, anthracene derivatives, benzophenone derivatives, chloranil and the like. The amount of addition is not particularly limited, but it is preferably used in the range of 0.01 to 300 parts by weight, preferably 0.1 to 100 parts by weight per 100 parts by weight of the photoacid generator. More preferably, the range of 0.5 to 50 parts by weight is most preferable. If the addition amount is less than 0.01 parts by weight, the effect cannot be sufficiently obtained, while if it exceeds 300 parts by weight, the weather resistance is lowered.

  The cyclic olefin-based (co) polymer composition of the present invention further includes 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 1,4-bis [(3-ethyl- 3-oxetanylmethoxy) methyl] benzene, di (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-oxetanylmethyl acrylate, 3-ethyl-3-oxetanylmethyl methacrylate, phenol novolac oxetane and the like Cationic polymerizable monomers selected from compounds, epoxy compounds such as bisphenol A diglycidyl ether and phenol novolac polyglycidyl ether can be added. By containing these and crosslinking together, the hardness, elastic modulus, breaking strength, etc. of the crosslinked product can be controlled, and chemical resistance and the like can be further improved. In such a composition, the blending ratio of the cyclic olefin-based (co) polymer of the present invention or the (co) polymer composition and the cationic polymerizable monomer is determined depending on the molecular structure, compatibility, and crosslinked product. Is suitably selected according to the purpose of use, but is preferably used in the range of 1 to 300 parts by weight per 100 parts by weight of the cyclic olefin-based (co) polymer.

  The cyclic olefin-based (co) polymer or the cyclic olefin-based (co) polymer composition of the present invention may also contain other thermoplastic resins such as a ring-opening (co) polymer and / or the (co) heavy. Combined hydride, addition copolymer of cyclic olefin and ethylene and / or α-olefin, polymethyl methacrylate, polyarylate, polyethersulfone, polyarylene sulfide, polyethylene, polypropylene, polyester, polyamide, petroleum resin, etc. It can also be used as a thermoplastic polymer composition blended with. In such a thermoplastic polymer composition, the blending ratio of the cyclic olefin-based (co) polymer of the present invention to the other (co) polymer is such that the cyclic olefin-based (co) polymer of the present invention and the other ( In order to obtain a (co) polymer composition having excellent heat resistance, the cyclic olefin of the present invention can be selected as appropriate depending on the type of co) polymer, the compatibility between the two, and the intended use of the composition. The proportion of the system (co) polymer is 5 to 95% by weight, preferably 10 to 90% by weight, and more preferably 20 to 80% by weight.

  The cyclic olefin-based (co) polymer of the present invention and the (co) polymer composition are obtained by hydrolyzing and condensing clay minerals such as silicon, aluminum, titanium and zirconium, montmorillonite, and alkoxysilane compounds. At least one metal oxide selected from silicon compounds and the like (hereinafter also referred to as “metal oxide”) may be blended to form a composite. As a method for producing these composites, a method of mixing in a solid state using a kneader, a solution of a cyclic olefin-based (co) polymer or a composition thereof and a metal oxide solvent dispersion are mixed, Before or after mixing the solution of cyclic olefin-based (co) polymer or composition thereof with tetraalkoxide, trialkoxide, dialkoxide such as silicon, aluminum, titanium, zirconium, etc. A method such as a “sol-gel method” for polycondensation, a metal oxide such as colloidal silica, alumina or titania, or a surface thereof modified with an acrylate ester or methacrylate ester having an alkoxysilyl group The method of mixing etc. is mentioned. In particular, when the cyclic olefin-based (co) polymer of the present invention contains an alkoxysilyl group, the metal oxide can be easily dispersed microscopically in the composite without the surface modification of the metal oxide. Can be easily obtained. The ratio of the metal oxide in the composite is used in a ratio of 5 to 70% by weight, and the particle diameter of the metal oxide is not uniquely determined. It becomes transparent when dispersed in diameter. As the proportion of the metal oxide having a particle diameter of 100 nm or more in the composite increases, the transparency decreases.

  The crosslinked olefin-based (co) polymer film of the present invention is a film comprising the cyclic olefin-based (co) polymer composition of the present invention heated at 0 to 150 ° C. for 0.1 to 100 minutes, Or it can obtain by making it bridge | crosslink by methods, such as irradiating active energy rays, such as an ultraviolet-ray and an electron beam. Although there is no restriction | limiting in particular in the source of the active energy ray used for bridge | crosslinking, The light of a wavelength of 200 nm-450 nm is used preferably. For example, it is desirable to irradiate the entire molded body using a high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, excimer lamp, etc., and also irradiate laser light or convergent light using lenses, mirrors, etc. Can do. Furthermore, it can also irradiate through the photomask which has the light transmissive part of a predetermined pattern. In addition, before and / or after the crosslinking reaction, pre-baking, post-baking, and heat curing can be performed as necessary.

The cyclic olefin-based (co) polymer of the present invention and the composition thereof can be formed into a molded body by a method such as injection molding, blow molding, press molding, extrusion molding, etc., and can also be a hydrocarbon solvent, halogenated hydrocarbon. A cyclic olefin-based (co) polymer can be dissolved in a solvent selected from polar solvents such as solvents, ketones, ethers, esters, amines, amides, ureas, etc., and then subjected to casting and evaporation steps to form thin films, films and sheets. it can. Moreover, after swelling a cyclic olefin type | system | group (co) polymer with these solvents, it can also shape | mold and process into a film and a sheet | seat, evaporating a solvent with an extruder. In these methods, it is preferable to use a casting method from a solution in order to suppress a crosslinking reaction due to heat particularly during molding.
In addition, in order to obtain a crosslinked film, sheet, or coating film, the cyclic olefin-based (co) polymer composition of the present invention is molded and processed, and then heated or irradiated with active energy rays to form a crosslinked body. It is preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The molecular weight, total light transmittance, glass transition temperature, linear expansion coefficient, and toluene swelling degree were measured by the following methods.

(1) Weight average molecular weight, number average molecular weight:
Using an H-type column manufactured by Tosoh Corporation with a 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS, the measurement was performed at 120 ° C. using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Total light transmittance:
Based on ASTM-D1003, a film having a thickness of 150 μm was used, and the total light transmittance was measured.
(3) Tan δ peak temperature (glass transition temperature):
The glass transition temperature of the (co) polymer was measured at the peak temperature of dynamic viscoelasticity Tan δ (ratio E ″ / E ′ = Tan δ of storage elastic modulus E ′ and loss elastic modulus E ″). Measurement of dynamic viscoelasticity using Leo Vibron DDV-01FP (manufactured by Orientec), measuring frequency 10Hz, heating rate 4 ° C / min, excitation mode single waveform, excitation amplitude 2.5μm Was obtained at the peak temperature of the temperature dispersion of Tan δ obtained using
(4) Linear expansion coefficient:
Using TMA (Thermal Mechanical Analysis) / SS6100 (manufactured by Seiko Instruments Inc.), a sample having a thickness of 100 μm, a width of 3 mm, and a length of 10 cm is fixed at a distance between chucks of 10 mm, and is temporarily raised from room temperature to about 200 ° C. After removing residual strain by warming, from room temperature to 3 ° C / min. The linear expansion coefficient was determined from the elongation of the distance between chucks.
(5) Toluene swelling degree:
A film having a thickness of 50 to 250 μm and a length and width of 1 cm × 2 cm was immersed in toluene at 25 ° C. for 3 hours, the film weight before and after the immersion was measured, and the degree of swelling was calculated by the following formula.
Toluene swelling degree (%) = (weight after toluene immersion / weight before toluene immersion) × 100

Synthesis Example 1: Synthesis of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene 3-Allyloxymethyl-3-ethyloxetane is described in J. Am. Macromol. Sci. Part A: Pure. Appl. Chem. , A30, 173-187 (1993). To a stainless steel autoclave with a capacity of 200 milliliters sufficiently substituted with nitrogen, 100 milliliters (0.59 mol) of 3-allyloxymethyl- ^3- ethyloxetane and tricyclo [4.3.0.1 ^2,5 ]. Deca-3,7-diene (dicyclopentadiene) was charged in an amount of 25 ml (0.19 mol). The valve was closed and heated at 170 ° C. for 2 hours. Further, 12 ml (0.09 mol) of tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene was added and heating for 2 hours was repeated twice. The obtained reaction mixture was transferred to a glass flask connected to a 200 mm Widmer type fractionating tube, and 78 g (yield 60) was obtained at a boiling point of 90 to 91 ° C. by distillation under reduced pressure at 0.1 mmHg. %)Obtained.

Synthesis Example 2: Synthesis of methyl bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl A cooling tube was connected to a 200 ml glass flask, and nitrogen was sufficiently added. Replaced. After adding 100 ml (0.61 mol) of acrylic acid (3-ethyl-3-oxetanyl) methyl and cooling to 0 ° C., 60 ml of cyclopentadiene obtained by thermal decomposition immediately before was added and stirred. While confirming a mild exotherm, the mixture was stirred for 6 hours while cooling so that the temperature did not exceed 10 ° C., and left overnight. Analysis by gas chromatography confirmed the disappearance of the raw acrylate compound, and 115 g (yield 80) with a purity of 99% or higher at a boiling point of 113 to 116 ° C. by distillation under reduced pressure at 0.1 mmHg. %).

Example 1
In a 200 ml pressure-resistant container made of glass that has been thoroughly dried and purged with nitrogen, 17 ml of bicyclo [2.2.1] hept-2-ene dissolved in dry toluene to a concentration of 5.79 mol / liter is dried. Toluene was charged in 50 ml, and further 1 mmol of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene obtained in Synthesis Example 1 was added. The temperature of the system was adjusted to 30 ° C. with stirring. 0.8 ml of a dry toluene solution (concentration: 0.05 mol / liter) of (η ⁶ -toluene) bis (pentafluorophenyl) nickel was added to initiate polymerization. After reacting for 60 minutes, the reaction was terminated by adding 0.4 g of lactic acid diluted with about 50 ml of toluene, dissolved in 4 ml of isopropyl alcohol, and further diluted with 20 ml of toluene. Washed twice with 30 ml of purified water, then coagulated in about 1 liter of isopropyl alcohol, dried under vacuum at 90 ° C. for 40 hours, and 7.7 grams (81% yield) of cyclic olefin copolymer Got. The weight average molecular weight (Mw) was 1,250,000, the number average molecular weight (Mn) was 570,000, and Mw / Mn was 2.2. In the analysis of the copolymer by ¹ H-NMR, the content of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene was 0.5 mol%. It was. Further, in the FT-IR spectrum of a film obtained by casting from a copolymer cyclohexane solution, absorption based on the oxetane skeleton was observed at 983 cm ⁻¹ .

Example 2
The same operation as in Example 1 was carried out except that the amount of added 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene was changed to 3 mmol, and 7 0.5 grams (yield 76%) of the copolymer was obtained. The weight average molecular weight (Mw) was 1,260,000, the number average molecular weight (Mn) was 500,000, and Mw / Mn was 2.5. In the analysis of the copolymer by ¹ H-NMR, the content of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene was 1.9 mol%. It was. Further, in the FT-IR spectrum of a film obtained by casting from a copolymer cyclohexane solution, sharp absorption based on the oxetane skeleton was observed at 985 cm ⁻¹ .

Example 3
The same operation as in Example 1 was carried out except that the amount of added 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene was changed to 5 mmol, and 7 0.0 grams (69% yield) of copolymer was obtained. The weight average molecular weight (Mw) was 1,400,000, the number average molecular weight (Mn) was 535,000, and Mw / Mn was 2.6. The content of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene in the analysis by ¹ H-NMR of the copolymer was 3.3 mol%. It was. Moreover, in the FT-IR spectrum of the film obtained by the casting method from the copolymer cyclohexane solution, sharp absorption based on the oxetane skeleton was observed at 986 cm ⁻¹ .

Example 4
Instead of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid ( The same operation as in Example 2 was carried out except that 3 mmol of 3-ethyl-3-oxetanyl) methyl was added to obtain 6.8 g (yield 69%) of the copolymer. The weight average molecular weight (Mw) was 1,000,000, the number average molecular weight (Mn) was 510,000, and Mw / Mn was 2.0. In the analysis of the copolymer by ¹ H-NMR, the content of bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl was 1.7 mol%. there were. Moreover, in the FT-IR spectrum of the film obtained by the casting method from the cyclohexane solution of the copolymer, the sharp and strong absorption based on the carbonyl group is 1,737 cm ⁻¹ , and the sharp absorption based on the oxetane skeleton is 1,150 cm ^−1. Respectively.

Reference example 1
In a 400-ml pressure-resistant container made of glass that has been sufficiently dried and purged with nitrogen, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 190 mmol of 1 ^7,10 ] -3-dodecene, ¹⁰ mmol of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene obtained in Synthesis Example 1 Toluene (200 ml) and molecular weight regulator 1-hexene (60 mmol) were added. WCl ₆ 0.02 mmol of the catalyst components, epichlorohydrin 0.04 mmol, initiate polymerization triethyl aluminum and 0.2 mmol, was carried out for 3 hours the polymerization while controlling the inside of the system to 50 ° C.. The polymerization was stopped by adding 0.4 mmol of benzaldehyde. Conversion of the monomer to the copolymer was 98%. The obtained copolymer solution was coagulated with methanol containing hydrochloric acid, further washed with methanol, and then dried at 50 ° C. for 17 hours. The content of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene in the analysis by ¹ H-NMR of the copolymer was 4.2 mol%. It was.

Next, 30 g of this copolymer was dissolved in 300 ml of toluene, 30 mg of carbonylchlorohydridotris (triphenylphosphine) ruthenium [RuHCl (CO) (PPh ₃ ) ₃ ] was added, 140 ° C., hydrogen pressure 8.0 MPa. A hydrogenation reaction was carried out for 4 hours to obtain a hydride of a copolymer. The resulting copolymer hydride solution was washed three times with 100 ml of a methanol / water mixture (50/50 volume ratio) containing 30 mmol of lactic acid, and further washed with 100 ml of water. Add 1 part by weight of the antioxidant pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate to 100 parts by weight of copolymer to the hydride solution of the copolymer. The hydride of the copolymer was coagulated with a large amount of methanol and dried at 80 ° C. for 17 hours. The weight average molecular weight was 176,000, and the number average molecular weight was 70,000. The hydrogenation rate was calculated to be 99.5% by ¹ H-NMR.

The ¹ H-NMR spectra of the copolymers obtained in Examples 1 to 4 and Reference Example 1 are shown in FIGS. 1 to 5, and the FT-IR spectra obtained in Examples 1 to 4 are shown in FIGS. 9 shows. In particular, in FIGS. 6 to 8, the absorption intensity at 983 to 986 cm ⁻¹ is a content ratio of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene. It can be seen that it increases according to.

Examples 6-10
Examples 1 to 4, 100 parts by weight of the copolymer obtained in Reference Example 1, and 3 parts by weight of di [4-alkyl (C10-C14) phenyl] iodonium hexafluoroantimonate (λ _max = 244 nm), As an antioxidant, pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-tert-butylphenyl) phosphite were each 0.9. A part by weight was added and cast from toluene or a cyclohexane-toluene mixed solution to prepare a film having a thickness of 150 μm, which was designated as F1 to F5. A sample piece of 1 × 2.5 centimeters was prepared from each of the obtained films, and evaluated after heating at 150 ° C. for 1 hour under vacuum. The results are shown in Table 1.
In addition, F1 to F5 obtained above were evaluated using a metal halide lamp as a light source, both surfaces of each film being irradiated with 300 mJ / cm ^{2 and} then heated at 150 ° C. under vacuum for 2 hours. The results are shown in Table 1. In any sample, the cross-linking proceeded to form a film insoluble in toluene. Examples corresponding to Examples 1 to 4 are Examples 6 to 9, and examples corresponding to Reference Example 1 are Example 10.

Comparative Example 1
The same procedure as in Example 1 was performed, except that 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene was not added, and 7.9 g (yield). A cyclic olefin polymer having a rate of 85%) was obtained. The weight average molecular weight (Mw) was 1,460,000, the number average molecular weight (Mn) was 610,000, and Mw / Mn was 2.4. About the obtained polymer, the cast film was created in the procedure of Examples 5-8, and the light irradiation by the metal halide lamp was performed, but the toluene swelling degree is 450% both before and after irradiation, and the crosslinking reaction is It did not progress at all.

Comparative Example 2
Instead of 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, 10 mmol of 5-ethylidenebicyclo [2.2.1] hept-2-ene The procedure of Example 1 was repeated except that 6.7 g (yield 61%) of a cyclic olefin copolymer was obtained. The weight average molecular weight (Mw) was 1,050,000, the number average molecular weight (Mn) was 403,000, and Mw / Mn was 2.6. About the obtained polymer, after making a cast film in the procedure of Examples 5-8, light irradiation with a metal halide lamp was performed, and it heated at 150 degreeC for 1 hour, but the film after irradiation is mostly toluene. Dissolved. In addition, instead of di [4-alkyl (C ₁₀ -C ₁₄ ) phenyl] iodonium hexafluoroantimonate, 1 part by weight of benzoyl peroxide was added to prepare a film and heated at 150 ° C. for 2 minutes. Most of the film was also dissolved in toluene.

  The film made of the cyclic olefin (co) polymer (composition) of the present invention and the crosslinked film have excellent heat resistance, optical properties, solvent resistance, chemical resistance, liquid crystal resistance, and homogeneity. In addition to liquid crystal display element substrates, electroluminescence display element substrates, various window materials, polarizing films, retardation films, liquid crystal films, antireflection films and other optical films, OHP films, printed circuit board substrates, etc. ) Polymers (compositions) are optical materials such as optical discs, optical fibers, lenses, prisms, optical filters, light guide plates, optical waveguides, electronic component materials such as semiconductor sealants, medical equipment, various containers, coating agents, and adhesives. It is suitably used for agents, binders and the like.

1 is a ¹ H-NMR spectrum of a cyclic olefin copolymer obtained in Example 1 in C ₆ D ₆ / o-dichlorobenzene. Cyclic olefin copolymer obtained in Example 2 _is the ¹ H-NMR spectrum of in C 6 _{D 6} 2 is a ¹ H-NMR spectrum in C ₆ D _{6 of} the cyclic olefin copolymer obtained in Example 3. FIG. 2 is a ¹ H-NMR spectrum in C ₆ D _{6 of} the cyclic olefin copolymer obtained in Example 4. FIG. 2 is a ¹ H-NMR spectrum in C ₆ D ₆ of a hydride of a cyclic olefin copolymer obtained in Reference Example 1. 2 is an IR spectrum of the cyclic olefin copolymer obtained in Example 1. 3 is an IR spectrum of the cyclic olefin copolymer obtained in Example 2. 3 is an IR spectrum of the cyclic olefin copolymer obtained in Example 3. 4 is an IR spectrum of the cyclic olefin copolymer obtained in Example 4.

Claims (8)

The number average molecular weight in terms of polystyrene is 5,000 including at least one structural unit derived from a cyclic olefin having an oxetane skeleton having an oxetanyl group represented by any one of the following general formulas (1) to (4). A film made of a cyclic olefin-based (co) polymer having ˜1,500,000.

[In the formulas (1) to (4), A ¹ , A ² and A ³ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group or a cycloalkyl group. is ^{(CR 6} R ₇₎ group selected from a polar group represented by _q Z - group, an aryl group or. Here, Z represents —OR ⁸ , —C (O) R ⁹ , —OC (O) R ¹⁰ , C (O) OR ¹¹ or —SiY ¹ Y ² Y ³ , and Y ^{1 to} Y ³ are the same or Differently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, an allyloxy group, a siloxy group, or a polyvalent one that forms a 5- to 8-membered ring by bonding to each other Represents an alcohol residue. X is a group which connects the cyclic olefin and an oxetanyl _{^{group, - (CR 12 R 13)}} r -, or _{^{- (CR 14 R 15) s}} -T- (CR 16 R 17) t - represents, T Represents —O—, —C (O) —, —OC (O) —, C (O) O—, —SiR ¹⁸ R ¹⁹ —. R ^{1 to} R ¹⁹ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, p and q are integers of 0 to 3, and r, s and t are 0 to 6 Represents an integer. ] The cyclic olefin system (co-polymer ) according to claim 1 , wherein the structural unit derived from the cyclic olefin having an oxetanyl group is at least one selected from those represented by the formula (1) or (2). ) A film made of a polymer. The film which consists of a cyclic olefin type | system | group (co) polymer of Claim 1 whose structural unit derived from the cyclic olefin which has an oxetanyl group is what is represented by the said Formula (1). Furthermore, the film which consists of a cyclic olefin type | system | group (co) polymer of any one of Claim 1 to 3 containing at least 1 sort (s) of the structural unit represented by either of the following general formula (5) or (6). .

[In the formula (5) or (6), B ¹ , B ² , B ³ , B ⁴ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group, A cycloalkyl group, an aryl group, a polar group represented by — (CR ²⁰ R ²¹ ) _v Z, an alkylidene group formed by B ¹ and B ² , an alkylene group in which B ¹ and B ³ are bonded, a cycloalkylene group, It is a group selected from an alkenylene group, a cycloalkenylene group and an arylene group, or a lactone or acid anhydride formed by ring closure of B ¹ and B ² or B ¹ and B ³ . R ²⁰ and R ²¹ are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and Z is the same as in formulas (1) to (4). u and v represent an integer of 0 to 3. ] Represented by general formula (1) (4), structural units derived from the cyclic olefin having an oxetanyl group, 4 any one of claims 1 contained 0.1 to 30 mol% in the total structural units A film comprising the cyclic olefin-based (co) polymer described in 1. A cyclic olefin-based (co) polymer composition comprising the cyclic olefin-based (co) polymer according to any one of claims 1 to 5 and an oxetanyl group ring-opening reaction initiator. A film consisting of The film comprising the photosensitive cyclic olefin-based (co) polymer composition according to claim 6 , wherein the oxetanyl group ring-opening reaction initiator is a photoacid generator. A crosslinked film of a cyclic olefin-based (co) polymer obtained by crosslinking a film comprising the cyclic olefin-based (co) polymer composition according to claim 6 or 7 .

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