JP3337153B2 - Cyclic olefin copolymer composition and film or sheet containing the composition as a main component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to packaging, automobiles, electricity,
Materials for various molded articles in the fields of electronics, medical care, agriculture, and the like, and a cyclic olefin-based copolymer composition that can be suitably used as a material for a film or a sheet, and a film containing the composition as a main component or Regarding the sheet.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins include:
BACKGROUND ART Resins such as high-density polyethylene, low-density polyethylene, and polypropylene are widely used in industrial and domestic fields. Many of these resins have high crystallinity and are excellent in mechanical properties, solvent resistance, electrical properties, etc., but lack the elastic recovery properties of soft polyvinyl chloride resin, etc., and when subjected to tensile stress, There is a problem that necking occurs and permanent distortion remains. In order to solve this problem, the present inventors have proposed a molded article made of a copolymer having excellent elastic recovery obtained by copolymerizing an α-olefin and a specific cyclic olefin (Japanese Patent Application No. Hei 10-276,878). 3-
99839).

[0003]

However, one of the features of the copolymer proposed here is that it has excellent elastic recovery and self-adhesiveness. However, there is a problem that the film cannot be smoothly formed into a film because of strong adhesion, and a carrier such as a release paper must be used when a sheet is produced by a T-die extrusion molding method. Further, there is a method of blending an additive such as a lubricant in order to reduce the tackiness. However, this method has a problem that the transparency of the film is significantly reduced and the appearance is impaired. The present invention has been made in view of the above problems, and has excellent mechanical properties and elastic recovery properties, and a cyclic olefin-based copolymer composition excellent in moldability such as a film and a composition containing the same as a main component. It is an object to provide a film or sheet containing

[0004]

According to the present invention, the following ring is provided.
Olefin copolymer (a) 100 parts by weight and a ring
Olefin copolymer (b) in an amount of 2 to 400 parts by weight
A cyclic olefin-based copolymer composition is provided. (A):Catalysts containing the following compounds (A) and (B) as main components
Medium or the following compounds (A), (B) and (C) as main components
Manufactured using a catalyst thatα-olefin and cyclic
Glass having repeating units derived from olefins
Cyclic olefins having a transition temperature (Tg) of 50 ° C. or less
Copolymer(A) containing a transition metal selected from Group IVB of the periodic table
Transition metal compounds (B) a transition metal compound (A) or a derivative thereof
Complex Compounds (C) Organoaluminum compound  (B): derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
0 ° C. or less and derived from a cyclic olefin
The cyclic olefin of the above (a) having a repeating unit content of
Repeating units derived from cyclic olefins
1 mol% or more, or 1 mol
% Or less small cyclic olefin copolymer

Also, 100 parts by weight of the cyclic olefin-based copolymer (a), 2 to 400 parts by weight of the cyclic olefin-based copolymer (b), 0.01% of an antiblocking agent and / or a lubricant. A cyclic olefin-based copolymer composition containing from 10 to 10 parts by weight is provided.

Furthermore, the following cyclic olefin copolymers
(A) 100 parts by weight and a cyclic olefin copolymer
(B) a ring containing 2 to 400 parts by weight
Containing a olefin-based copolymer composition as a main component,
That the tensile modulus is less than 3,000 kg / cm ²
A feature film or sheet is provided. (A): derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
Cyclic olefin copolymer (b) having a temperature of 0 ° C. or lower : derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
0 ° C. or less and derived from a cyclic olefin
The cyclic olefin of the above (a) having a repeating unit content of
Repeating units derived from cyclic olefins
1 mol% or more, or 1 mol
% Or less small cyclic olefin copolymer

Hereinafter, the present invention will be described specifically. 1. Cyclic olefin copolymer (a) Cyclic olefin copolymer (a) used in the present invention
Has a repeating unit derived from an α-olefin and a cyclic olefin. Here, the α-olefin is not particularly limited, but may be, for example, the following general formula [X]

Embedded image (In the formula [X], Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

In the α-olefin repeating unit represented by the general formula [X], Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms as described above.
Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-butyl group, an n-hexyl group, an octyl group, and an octadecyl group. be able to. Specific examples of the α-olefin that gives the α-olefin repeating unit represented by the general formula [X] include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1 -Pentene, 1-hexene, 1-octene, decene, eicosene and the like.

The cyclic olefin is not particularly limited, but may be, for example, a compound represented by the following general formula [Y]:

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. )).

In the cyclic olefin repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom or an oxygen atom, as described above. Alternatively, a substituent containing a nitrogen atom is shown. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, n
1 to 2 carbon atoms such as -propyl, isopropyl, n-butyl, isobutyl, t-butyl, hexyl, etc.
An alkyl group having 6 to 20 carbon atoms such as an alkyl group having 0, a phenyl group, a tolyl group, and a benzyl group; an alkylidene group having 1 to 20 carbon atoms such as a methylidene group, an ethylidene group, and a propylidene group; And an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group. Where R ^b , R ^c , R
^f and R ^g exclude an alkylidene group. Note that R ^d , R ^e , and R ^h
If any of to R ^m is an alkylidene group, the carbon atom to which it is attached does not have the other substituent.

Specific examples of the substituent containing a halogen atom include halogen substituents having 1 to 20 carbon atoms such as a halogen group such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specific examples of the substituent containing a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the repeating unit of the cyclic olefin represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, Methyl norbornene, 7-methyl norbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-
Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned.

The cyclic olefin-based copolymer (a) is basically composed of the α-olefin component and the cyclic olefin component as described above, but these are not detracted from the object of the present invention. In addition to the essential two components, other copolymerizable unsaturated monomer components may be contained as necessary. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above-mentioned α-olefin components, those not previously used, among the above-mentioned cyclic olefin components, Those not used,
Examples thereof include cyclic dienes such as dicyclopentadiene and norbornadiene, chain dienes such as butadiene, isoprene and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin-based copolymer (a) is α-
Regarding the content [x] of the olefin unit and the content [y] of the cyclic olefin unit, [x] is 80 to 99.9 mol%.
[Y] is preferably 20 to 0.1 mol%, and particularly [x] is 82 to 99.5 mol%, and [y] is 18 to 0.5 mol%, and especially [x] is 85 to 98 mol%
[Y] is more preferably 15 to 2 mol%. α-olefin unit content [x] is 80 mol%
If it is less than 3, the glass transition temperature (Tg) and the tensile modulus of the copolymer become high, and the obtained copolymer composition and the elastic recovery property of a film or sheet containing the same as a main component and molding of a molded product are obtained. The product may have insufficient impact resistance and elasticity. On the other hand, when the content of the cyclic olefin unit [y] is less than 0.1 mol%, the crystallinity of the copolymer increases, and the effect of introducing the cyclic olefin component such as elastic recovery becomes insufficient. The cyclic olefin-based copolymer (a) is a substantially linear copolymer in which α-olefin units and cyclic olefin units are linearly arranged and does not have a gel-like crosslinked structure. preferable. The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The cyclic olefin copolymer (a) must have a glass transition temperature (Tg) of 50 ° C. or less. By using such a copolymer, it is possible to obtain a copolymer composition that can be suitably used at a low temperature, and a film, a sheet, a molded article, and the like containing the copolymer composition as a main component. A preferred glass transition temperature (Tg) is -30
To 40 ° C, more preferably -30 to 35 ° C. In this case, the glass transition temperature (Tg) of the cyclic olefin-based copolymer (a) can be arbitrarily controlled by changing the type and composition of the monomer. The glass transition temperature (Tg) can be arbitrarily changed according to the conditions.

The cyclic olefin-based copolymer (a) contains 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.01
It is preferably ２０20 dl / g. Intrinsic viscosity [η]
If it is less than 0.01 dl / g, the strength may be significantly reduced, and if it exceeds 20 dl / g, the moldability may be significantly deteriorated. More preferable intrinsic viscosity [η] is 0.1.
05 to 10 dl / g.

The cyclic olefin copolymer (a) preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. When the crystallinity exceeds 40%, elastic recovery and transparency may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer (a) preferably has a tensile modulus of less than 3,000 kg / cm ² . When the tensile elastic modulus is 3,000 kg / cm ² or more, for example, when a packaging film is formed with the composition of the present invention, a great amount of energy is required at the time of packaging, and a beautiful shape adapted to the shape of the article to be packaged. Packaging may be difficult. Further, when a molded article is formed, impact resistance may be insufficient. A more preferred tensile modulus is 50 to 2,000 kg / cm ² .

The cyclic olefin copolymer (a) preferably has an elastic recovery of at least 20%. When the elastic recovery is less than 20%, for example, when the article is wrapped with a film comprising the composition of the present invention, sagging occurs,
The holding power may decrease. A more preferable elastic recovery rate is 30% or more, particularly 40% or more. The elastic recovery rate is a value obtained by a measurement method described in Examples described later.

The cyclic olefin copolymer (a) has a DS
Broad melting peak due to C (heating measurement) is 100 ° C
It is preferably less than. A copolymer having a sharp melting peak at 100 ° C. or higher by DSC (temperature rise measurement) has a wide composition distribution of the copolymer of cyclic olefin and α-olefin, and the elastic recovery of the molded product is insufficient. It may be. In addition, it is more preferable that the broad melting peak by DSC (temperature rise measurement) is in the range of 10 to 95 ° C. In DSC (temperature rise measurement), the melting point (melting peak) of the olefin-based copolymer cannot be seen sharply. No peak appears. Due to the characteristics of the thermal properties described above, the physical properties of the molded article can be obtained, and the molded article can be molded stably, for example, the molding temperature range is widened.

The cyclic olefin-based copolymer (a) may be a copolymer consisting of only those having the physical properties in the above-mentioned range, and some copolymers having physical properties outside the above-mentioned range are included. May be used. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the cyclic olefin copolymer (a) is not particularly limited, but the following compounds (A) and (B)
Is efficiently produced by copolymerizing an α-olefin and a cyclic olefin using a catalyst mainly composed of, or a catalyst mainly composed of the following compounds (A), (B) and (C). be able to. (A) a transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) a compound capable of forming an ionic complex from the transition metal compound (A) or a derivative thereof (C) an organoaluminum compound

In this case, the compound (A) may be any compound containing a transition metal selected from Group IVB of the periodic table, ie, titanium (Ti), zirconium (Zr) or hafnium (Hf). Although it is also possible to use a compound represented by the following general formula (I), (II) or (III), a cyclopentadienyl compound or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is particularly preferable. It is.

CpM ¹ R ¹ _a R ² _b R ³ _c (I) Cp ₂ M ¹ R ¹ _d R ² _e (II) (Cp-A _f -Cp) M ¹ R ¹ _d R ² _e ( III) M ¹ R ¹ _g R ² _h R ³ _i R ⁴ _j (IV) [In the formulas (I) to (IV), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group. R
¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an oxygen atom,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 1 carbon atom
An alkoxy group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group or arylalkyl group, acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen A ligand such as a molecule, a Lewis base, a chain unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon is shown, and A represents a crosslink by a covalent bond. a, b and c are each an integer of 0-3, d and e are each an integer of 0-2, f is an integer of 0-6, and g, h, i and j are each an integer of 0-4. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
Examples thereof include a 4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and a trimethylsilylcyclopentadienyl group. Specific examples of R ^{1 to} R ⁴ include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom;
Methyl, ethyl, n-propyl, iso-propyl, n-butyl, octyl,
2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; phenyl group, tolyl as C6-C20 aryl group, alkylaryl group or arylalkyl group Group, xylyl group, benzyl group;
A heptadecylcarbonyloxy group as an acyloxy group of 20; a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, ethers such as tetrahydrofuran as Lewis bases, thioethers such as tetrahydrothiophene, ethyl Esters such as benzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine,
Amines such as N, N-dimethylaniline, pyridine, 2,2′-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine;
As chain unsaturated hydrocarbons, ethylene, butadiene, 1-
Pentene, isoprene, pentadiene, 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof; Can be. Examples of the crosslink by the covalent bond of A include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclopentane Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium,

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Alternatively, a zirconium compound having one or more of an alkyl group, an alkoxy group, and a halogen atom such as a compound in which zirconium is replaced with hafnium or titanium, a hafnium compound, or a titanium compound can be given. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetraphenoxy zirconium, tetrakis (2-ethylhexyloxy) zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro zirconium, dibutoxy dichloro zirconium Bis (2,6-di-t-butylphenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy) dichlorozirconium, zirconium tetrakis (acetylacetonate)

The compound (B) is not limited, but may be an ionic compound (B-B) capable of forming an ionic complex from the transition metal compound (A) or a derivative thereof.
1) Specifically, compounds represented by the following formula (V) or (VI) can be suitably used. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or ^{R 11 M 6) [(V} ), (VI) formula Where L ¹ is a Lewis base, M ³ and M ⁴
Are VB, VIB, VIIB, and VIII of the periodic table, respectively.
Group, IB, IIB, Group IIIA, elements selected from Group IVA, and group VA, of M ⁵ and M ^6, respectively Periodic Table IIIB
Group, IVB group, VB group, VIB group, VIIB group, VIII group, IA
Group, IB group, IIA group, an element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid It represents a group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and R ⁸ and R ⁹ each represent a cyclopentadienyl group or a substituted cyclopentane. dienyl group, an indenyl group or a fluorenyl group, R ¹⁰ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. m is a valence of M ³ or M ⁴ and is an integer of 1 to 7, n is an integer of 2 to 8, and k is [L ¹ −
R ⁷ ] and [L ² ] are ionic valences and are integers of 1 to 7, and p is 1
The above integer, q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p- bromo- N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, ethyl
Esters such as Rubenzoeto, and the like can be given. Specific examples of M ³ and M ⁴ include B, Al, Si, P,
As, Sb and the like, Li Specific examples of M ^5, Na, A
g, Cu, Br, I, I 3 , etc., specific examples of M ⁶ M
n, Fe, Co, Ni, Zn and the like.
Z ¹ Specific examples of the to Z ^n, for example, dimethylamino group as a dialkylamino group, a diethylamino group; methoxy group as alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group; C6-20 Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as aryloxy group; methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n as alkyl group having 1 to 20 carbon atoms -Octyl group, 2-ethylhexyl group; a phenyl group as an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, p
-Tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-
Dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,
5-trifluorophenyl group, pentafluorophenyl group, 3,5- bis (trifluoromethyl) phenyl group;
Examples of the halogen atom include F, Cl, Br, and I. Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those described above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. here,
The alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 4.

Among the compounds of the formulas (V) and (VI), M ³ ,
Those in which M ⁴ is boron are preferred. Among the compounds of the formulas (V) and (VI), the following compounds can be used particularly preferably. Compound of formula (V): Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methylphenylphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethyltetraphenylborate Honiumu, tetrakis (pentafluorophenyl) borate triethylammonium tetrakis (pentafluorophenyl) borate tri (n-
Butyl) ammonium tetrakis (pentafluorophenyl) borate triphenyl ammonium, tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate (tetraethylammonium) tetrakis (pentafluorophenyl) borate (methyltri (n- butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n- butyl) ammonium), tetrakis (pentafluorophenyl) borate methyldiphenyl ammonium tetrakis (pentafluorophenyl) borate methyltriphenylphosphonium ammonium tetrakis (pentafluorophenyl ) borate dimethyl diphenyl ammonium tetrakis (pentafluorophenyl) borate anilinium, Tetoraki (Pentafluorophenyl) borate-methyl anilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate trimethyl anilinium tetrakis (pentafluorophenyl) borate dimethyl (m-nitro anilinium), tetrakis ( pentafluorophenyl) borate dimethyl (p- bromo anilinium), tetrakis (pentafluorophenyl) borate pyridinium tetrakis (pentafluorophenyl) borate (p- cyanopyridinium) tetrakis (pentafluorophenyl) borate (N- methylpyridinium) , tetrakis (pentafluorophenyl) borate (N- benzyl pyridinium), tetrakis (pentafluorophenyl) borate (O-cyano -N- methylpyridinium , Tetrakis (pentafluorophenyl) borate (p- cyano -N- methylpyridinium) tetrakis (pentafluorophenyl) borate (p- cyano -N- benzyl pyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium tetrakis (penta Benzyldimethylsulfonium fluorophenyl) borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenate
Nyl] dimethylanilinium borate, triethylammonium hexafluoroarsenate,

[0033]Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin man
gun),Tetrakis (Pentafluorophenyl) borate ferroseni
Umm,Tetrakis (Pentafluorophenyl) decamethyl borate
Ferrocenium,Tetrakis (Pentafluorophenyl) acetyl borate
Erosenium,Tetrakis (Pentafluorophenyl) formylph borate
Erosenium,Tetrakis (Pentafluorophenyl) cyanofe borate
Rosenium,Tetrakis (Pentafluorophenyl) silver borate,Tetrakis (Pentafluorophenyl) trityl borate,Tetrakis Lithium (pentafluorophenyl) borate,Tetrakis Sodium (pentafluorophenyl) borate
,Tetrakis (Pentafluorophenyl) boric acid (tetraf
Enylporphyrin manganese),Tetrakis (Pentafluorophenyl) boric acid (tetraf
Enylporphyrin iron chloride),Tetrakis (Pentafluorophenyl) boric acid (tetraf
Zinc porphyrin), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate, and compounds other than formulas (V) and (VI), for example,Tris
(Pentafluorophenyl) boron,Tris [3,5-bi
[(Trifluoromethyl) phenyl]Boron, Trifeni
Leboron or the like can also be used. Further, as compound (B)
Is methylaluminoxane, ethylaluminoxane, i
Sobutylaluminoxane, chloro-containing alkylalumino
Organoaluminum oxy compounds such as xane (B-2)
Can also be used. Degree of polymerization of this aluminoxane
Is 3 to 50, preferably 5 to 30.

As the organoaluminum compound as the component (C), there can be mentioned those represented by the following general formula (VII) . R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, Q is a hydrogen atom, Represents a halogen atom or an alkoxy group having 1 to 20 carbon atoms, where r is 1 ≦ r ≦ 3
Of the range. Specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. It is.

The above-mentioned catalyst can be used as the component (A) and the component (B) [(B-1) or (B-2)], or the component (A) and the component (B) [(B-1)]. Component and component (C) as main components. In this case, the use conditions of the component (A) and the component (B-1) are not limited,
Component: The ratio (molar ratio) of component (B-1) is 1: 0.01 to
The ratio is preferably set to 1: 100, particularly 1: 1 to 1:10. The conditions for using the component (A) and the component (B-2) are as follows: component (A): component (B-2) (molar ratio as a metal atom) in the range of 1:10 to 1: 10,000, particularly 1 : 20 ~
The ratio is preferably set to 1: 5,000. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily. Also, (C)
The amount of the component is usually from 0 to 2 per mole of the component (A).
000 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the copolymer, which is not preferable. The components (A) and (B) may be brought into contact in advance, and the contact product may be separated and washed before use, or may be used after being brought into contact in a polymerization system. The component (C) is a component (A),
It may be used in contact with the component (B) or the contact product of the component (A) and the component (B). The contact may be made in advance, or may be brought into contact in the polymerization system.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250C, particularly preferably -50 to 200C. The ratio of the catalyst to the reaction raw material is such that the raw material monomer / component (A) (molar ratio) or the raw material monomer / component (B) (molar ratio) is 1 to 1.
0 ^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is from normal pressure to
100 kg / cm ² G, preferably normal pressure to 50 kg / c
m ² G. As a method of adjusting the molecular weight of the copolymer,
The amount of each catalyst component used, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be performed.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and fats such as pentane, hexane, heptane and octane Group hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in a combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

2. Cyclic olefin copolymer (b) As the cyclic olefin copolymer (b) used in the present invention, the same as the cyclic olefin copolymer (a) except for the following points can be used. That is,
It is necessary that the content of the cyclic olefin unit [y] is at least 1 mol% or more or at least 1 mol% smaller than the cyclic olefin copolymer (a). It is preferably 1.5 to 15 mol% large or small, and 2 to 12 mol%.
More preferably, the molar percentage is large or small.

The cyclic olefin copolymer composition of the present invention comprises the cyclic olefin copolymer (b) in a proportion of 2 to 400 parts by weight based on 100 parts by weight of the cyclic olefin copolymer (a). It is blended. If the proportion of the cyclic olefin-based copolymer (b) is outside the above range, the effect of improving moldability is low, and a good film or sheet cannot be obtained. The proportion of the cyclic olefin copolymer (b) is preferably 3 to 300 parts by weight,
It is particularly preferred that the amount be 5 to 200 parts by weight.

3. Anti-blocking agent and lubricant In the present invention, it is preferable to use 0.01 to 10 parts by weight of an anti-blocking agent and / or a lubricant,
-8 parts by weight is more preferable, and 0.05-5 parts by weight is particularly preferable. If it is less than 0.01 parts by weight, the tackiness is large,
Stable molding cannot be performed, and if it exceeds 10 parts by weight, transparency is reduced.

The type of the antiblocking agent is not particularly limited, and examples thereof include metal oxides, fluorides, nitrides, sulfates, phosphates, carbonates, and composite salts thereof. Specifically, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, aluminosilicate, zeolite, diatomaceous earth, talc, kaolinite, sericite, montmorillonite, hectorite, calcium fluoride, magnesium fluoride, boron nitride, nitrided Examples include aluminum, calcium sulfate, strontium sulfate, barium sulfate, calcium phosphate, strontium phosphate, barium phosphate, calcium carbonate, strontium carbonate, and barium carbonate.

The type of the lubricant is not particularly limited, and one or two or more lubricants such as higher aliphatic hydrocarbons, higher fatty acids, fatty acid amides, fatty acid esters, fatty acid alcohols and polyhydric alcohols may be used. Can be. Specific examples of the lubricant include liquid paraffin, natural paraffin, polyethylene wax, fluorocarbon oil, lauric acid, palmitic acid, stearic acid, iristearic acid, hydroxylauric acid, hydroxystearic acid,
Oleic acid amide, lauric acid amide, erucic acid amide, methyl stearate, butyl stearate, stearyl alcohol, cetyl alcohol, isocetyl alcohol, ethylene glycol, diethylene glycol, fatty acid monoglyceride and the like can be suitably used.

It should be noted that only one of the anti-blocking agent and the lubricant may be used, or both may be used in combination.

The cyclic olefin polymer composition of the present invention may further contain, if necessary, other additives such as stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants,
Inorganic and organic fillers, dyes, pigments and the like may be added.

The method for producing the cyclic olefin polymer composition of the present invention is not particularly limited, but it can be favorably produced by kneading each component in a molten state. As the melt-kneading apparatus, conventionally known apparatuses such as an open-type mixing roll, a non-open-type Banbury mixer, an extruder, a kneader, and a continuous mixer can be used. In addition, a method of adding an additive to a master batch made of a cyclic olefin-based copolymer can also be preferably employed.

The olefin polymer composition of the present invention can be formed into films, sheets, and various molded articles by well-known methods. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixed extruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder Extrusion molding, injection molding, compression molding, blow molding, rotational molding, etc. are performed using a screwless extruder or the like. Further, a film or a sheet can be prepared by a T-die molding method, an inflation molding method, or the like. In addition, if necessary, it is also possible to carry out molding directly during the production of the composition.

The olefin polymer composition of the present invention has transparency, elastic recovery, tackiness, piercing strength, tear strength,
Excellent in various properties such as weather resistance, low temperature heat sealability, heat seal strength, impact strength, shape memory, dielectric properties, etc., for example, sealant film, pallet stretch film, commercial wrap film, agricultural film, meat packaging It can be used for various applications such as films, shrink films, coating materials, vibration damping materials, pipes, medical infusion packs, and toys. In particular, when a film or sheet, elastic recovery, transparency, while having excellent adhesion,
It is possible to obtain a film or sheet that is hardly blocked and can be effectively used in various fields such as packaging, medical treatment, and agriculture.

[0048]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Reference Example 1 (Copolymerization of ethylene and 2-norbornene) Under a nitrogen atmosphere, at room temperature, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 micromol of zirconium tetrachloride, tetrakis (pentafluoro) in a 30 liter autoclave at room temperature. 60 micromoles of anilinium phenyl) borate are charged in this order, followed by 2.9 liters of a toluene solution containing 70% by weight of 2-norbornene (19 liters as 2-norbornene).
Mol) was added. After the temperature was raised to 80 ° C., the reaction was carried out for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7.5 kg / cm ² . After the completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. The polymer is filtered and dried,
A cyclic olefin copolymer (a1) was obtained. The yield of the cyclic olefin copolymer (a1) was 3.21 kg. The polymerization activity was 928 kg / gZr.

The obtained cyclic olefin copolymer (a
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of a peak based on ethylene and a peak based on methylene at the 5- and 6-positions of norbornene appearing at around 3 ppm and 3
The norbornene content determined from the ratio to the peak based on a methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 10.1 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.03 dl / g, and the crystallinity determined by X-ray diffraction was 2.0%. Vibron 11-EA manufactured by Toyo Bolding Co., Ltd. as a measuring device
Using a mold, a test piece having a width of 4 mm, a length of 40 mm, and a thickness of 0.1 mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. When the transition temperature (Tg) was determined, the Tg was 4 ° C.
ALC / GPC150 manufactured by Waters as a measurement measure
C, 1,2,4-trichlorobenzene solvent, 13
When the weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were determined at 5 ° C. in terms of polyethylene, Mw was 62,300, Mn was 33,900, and Mw / Mn.
Mn was 1.84. Using a Perkin Elmer 7 series DSC at a rate of 10 ° C./min, -50
When the melting point (Tm) was measured in the range of ℃ ~ 150 ℃,
Tm was 78 ° C. (broad peak).

Reference Example 2 (copolymerization of ethylene and 2-norbornene) In Reference Example 1, the amount of zirconium tetrachloride was reduced to 75
Micromolar, tetrakis (pentafluorophenyl)
The amount of anilinium borate used was 150 μmol,
The amount of norbornene used was 7.5 mol and the ethylene partial pressure was 6
and kg / cm ^2, and the polymerization temperature except that a 90 ° C., was obtained in the same manner as in Reference Example 1 cycloolefin copolymer (a2). The yield of the cyclic olefin copolymer (a2) was 2.66 kg. The polymerization activity is 389 kg /
gZr. The norbornene content obtained in the same manner as in Reference Example 1 was 5.2 mol%, and the intrinsic viscosity [η] was 1.
17 dl / g, crystallinity 4.7%, Tg 0 ° C., Mw
Was 73,600, Mn was 36,400, Mw / Mn was 2.02, and Tm was 92 ° C (broad peak).

Example 1 The cyclic olefin copolymer (a) obtained in Reference Example 1 was used.
30 parts by weight of the pellet of the cyclic olefin copolymer (a2) obtained in Reference Example 2, 0.6 parts by weight of diatomaceous earth as an antiblocking agent, and erucamide as a lubricant with respect to 100 parts by weight of the pellet of 1) 0.2 parts by weight of
It was fed to a 50 mm diameter single screw extruder. 100m diameter
extruded at 160 ° C from an annular die having a gap of 3 mm and a thickness of 20 μm by inflation molding.
A 40 mm film was obtained. The discharge rate was 7 kg / hr, and the pulling speed was 6.0 m / min. The moldability was good. Table 1 shows the results of measuring physical properties such as tensile properties, elastic recovery properties, and optical properties of the obtained films.

Here, the measurement of each item was performed as follows. Tensile modulus: JIS-K7113 using autograph
Was performed according to Tensile breaking strength: JIS-K711 using an autograph
3 was performed. Tensile elongation at break: JIS-K711 using autograph
3 was performed. Elastic recovery rate: Using an autograph, a tensile speed of 62 mm /
In a minute, a measuring piece having a width of 6 mm and a distance of 50 mm (L ₀ ) between clamps is stretched by 150%, pulled and kept as it is for 5 minutes. The length (L ₁ ) was measured and determined by the following equation. Elastic recovery rate (%) = [1-{(L ₁ −L ₀ )}] × 10
0 In this case, a good elastic recovery rate is 10% or more, particularly 30%.
As mentioned above, it is 60% or more especially. Haze: DIGITAL HA
ZE COMPUTER) (Suga Test Machine Co., Ltd.)
The measurement was performed according to S-K7105. Heat seal temperature: A test piece of 4 cm × 20 cm was heat-sealed at a width of 10 mm × 15 mm and a pressure of 2 kg / cm ² .
After pressure bonding for 2 seconds and heat sealing, it was left for 30 minutes, and the peel strength at a pulling speed of 200 mm / min was 300 g.
Temperature.

Examples 2 to 4 and Comparative Example 1 Films were obtained in the same manner as in Example 1 except that the amounts of the components were changed as shown in Table 1. Table 1 shows the results of the physical property measurement.

Example 5 The cyclic olefin copolymer (a) obtained in Reference Example 1 was used.
30 parts by weight of the pellet of the cyclic olefin copolymer (a2) obtained in Reference Example 2, 0.6 parts by weight of diatomaceous earth as an antiblocking agent, and erucamide as a lubricant with respect to 100 parts by weight of the pellet of 1) 0.2 parts by weight of
Extruded at 190 ° C from a T-die having a width of 500 mm and a gap of 1 mm, and cast to a thickness of 15 μm and a width of 400.
m was obtained. The discharge rate was 3 kg / hr, the tensile speed was 5 m / min, and the moldability was good. Table 1 shows the measurement results of the physical properties of the obtained film.

Examples 6 to 8 and Comparative Example 2 Films were obtained in the same manner as in Example 1 except that the amounts of the components were changed as shown in Table 1. Table 1 shows the results of the physical property measurement.

[0056]

[Table 1]

[0057]

According to the present invention, a cyclic olefin copolymer composition having excellent mechanical properties and elastic recovery properties and excellent moldability such as a film, and a film containing the composition as a main component are provided. Sheets can be provided.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08F 4/64-4/69

Claims (5)

(57) [Claims] 1. The following cyclic olefin copolymer (a) 1
00 parts by weight and the cyclic olefin copolymer (b) 2
Cyclic olef, characterized by containing 〜400 parts by weight
In-based copolymer composition. (A):Catalysts containing the following compounds (A) and (B) as main components
Medium or the following compounds (A), (B) and (C) as main components
Manufactured using a catalyst thatα-olefin and cyclic
Glass having repeating units derived from olefins
Cyclic olefins having a transition temperature (Tg) of 50 ° C. or less
Copolymer(A) containing a transition metal selected from Group IVB of the periodic table
Transition metal compounds (B) a transition metal compound (A) or a derivative thereof
Complex Compounds (C) Organoaluminum compound  (B): derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
0 ° C. or less and derived from a cyclic olefin
The cyclic olefin of the above (a) having a repeating unit content of
Repeating units derived from cyclic olefins
1 mol% or more, or 1 mol
% Or less small cyclic olefin copolymer 2. The cyclic olefin-based copolymer (a)
100 parts by weight and a cyclic olefin-based copolymer (b)
The cyclic olefin copolymer composition according to claim 1, comprising 2 to 400 parts by weight and 0.01 to 10 parts by weight of an antiblocking agent and / or a lubricant. 3. A film or sheet comprising the cyclic olefin copolymer composition according to claim 1 or 2 as a main component. 4. The following cyclic olefin copolymer (a) 1
00 parts by weight and cyclic olefin copolymer (b) 2
Cyclic olef, containing from 0.5 to 400 parts by weight
It contains an epoxy copolymer composition as a main component and has tensile elasticity.
The rate is 3,000kg / cm ^Two Less than
Film or sheet.  (a): Derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
Cyclic olefin copolymer having a temperature of 0 ° C. or lower (B): derived from α-olefin and cyclic olefin
Having a glass transition temperature (Tg) of 5
0 ° C. or less and derived from a cyclic olefin
The cyclic olefin of the above (a) having a repeating unit content of
Repeating units derived from cyclic olefins
1 mol% or more, or 1 mol
% Or less small cyclic olefin copolymer 5. The tensile modulus is 800 kg / cm. ^Two Less than
The film or claim according to claim 4,
Is a sheet.