JPH06271724A - Cycloolefinic polymer composition and film or sheet mainly made of this composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which is excellent in moldability and can give a molding excellent in mechanical properties, elastic recovery, etc., by blending two specified cycloolefinic copolymers with each other in a specified weight ratio. CONSTITUTION:This polymer composition is produced by mixing 100 pts.wt. cycloolefinic copolymer having repeating units derived from an alpha-olefin (e.g. ethylene) and repeating units derived from a cycloolefin (e.g. norbornene) and having a glass transition temperature of 50 deg.C or below with 2-400 pts.wt. cycloolefinic copolymer having repeating units derived from an alpha-olefin and repeating units derived from a cycloolefin and having a glass transition temperature of 50 deg.C or below, a content of the repeating units derived from the cycloolfin larger or smaller by at least 1mol% than the content of the repeating units derived from the cycloolefin of the former copolymer.

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, medicine, agriculture, etc., and a cyclic olefin-based copolymer composition that can be suitably used as a material for a film or sheet, and a film containing the composition as a main component. Regarding the seat.

[0002]

2. Description of the Related Art Conventionally, as a polyolefin resin,
Resins such as high-density polyethylene, low-density polyethylene and polypropylene are widely used in both industrial and household fields. Many of these resins have high crystallinity and are excellent in mechanical properties, solvent resistance, electrical properties, etc., but lack the elastic recovery of soft polyvinyl chloride resin, etc., and when subjected to tensile stress. There was a problem that necking occurred and permanent distortion remained. In order to solve this problem, the present inventors have proposed a molded article composed of a copolymer having an excellent elastic recovery property obtained by copolymerizing an α-olefin with a specific cyclic olefin (Japanese Patent Application No. Hei 10-135242). 3-
99839).

[0003]

However, one of the features of the copolymer proposed here is that it has excellent elastic recovery and self-adhesive properties. However, in the case of inflation molding of a thin film, However, there is a problem in that the adhesiveness is so strong that a film cannot be formed smoothly, and that a carrier such as release paper has to be used when a sheet is produced by the T-die extrusion molding method. Further, there is a method of blending an additive such as a lubricant in order to reduce the tackiness, but this causes a problem that the transparency of the film is significantly lowered and the appearance is impaired. The present invention has been made in view of the above-mentioned problems, and is excellent in mechanical properties and elastic recovery properties, and a cyclic olefin-based copolymer composition excellent in molding processability of a film or the like and its composition as a main component. The present invention aims to provide a film or sheet containing

[0004]

According to the present invention, a cyclic olefin copolymer containing 100 parts by weight of the following cyclic olefin copolymer (a) and 2 to 400 parts by weight of the cyclic olefin copolymer (b). A polymer composition is provided. (A): having a repeating unit derived from α-olefin and cyclic olefin and having a glass transition temperature (Tg) of 5
Cyclic olefin-based copolymer having a temperature of 0 ° C. or lower (b): having a repeating unit derived from α-olefin and a cyclic olefin, and having a glass transition temperature (Tg) of 5
The content of repeating units derived from a cyclic olefin at 0 ° C. or lower is 1 mol% or more than the content of repeating units derived from a cyclic olefin of the cyclic olefin copolymer of (a) above. Cyclic olefin copolymer having a large amount or a small amount of 1 mol% or more

Further, 100 parts by weight of the above-mentioned cyclic olefin copolymer (a), 2 to 400 parts by weight of the cyclic olefin copolymer (b), 0.01 anti-blocking agent and / or 0.01 lubricant. A cyclic olefin-based copolymer composition containing 10 to 10 parts by weight is provided.

Further, there is provided a film or sheet containing the cyclic olefin copolymer composition as a main component.

The present invention will be specifically described below. 1. Cyclic Olefin Copolymer (a) Cyclic Olefin Copolymer (a) Used in the Present Invention
Have repeating units derived from α-olefins and cyclic olefins. Here, the α-olefin is not particularly limited, but for example, the following general formula [X] is used.

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

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

The cyclic olefin is not particularly limited, but for example, the following general formula [Y]

[Chemical 2] (In the formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) Which has the repeating unit represented by these.

In the repeating unit of the cyclic olefin represented by the above general formula [Y], R ^{b to} R ^m are, as described above, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or an oxygen atom, respectively. Alternatively, it represents a substituent containing a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group and the like having 1 to 2 carbon atoms
C6-C20 aryl group such as 0 alkyl group, phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl group, alkylidene group having 1-20 carbon atoms such as methylidene group, ethylidene group and propylidene group , An alkenyl group having 2 to 20 carbon atoms such as vinyl group and allyl group. However, R ^b , R ^c , R
^f and R ^{g do not} include an alkylidene group. Note that R ^d , R ^e , and R ^h
When any of R ^m is an alkylidene group, the carbon atom to which it is attached has no other substituents.

Specific examples of the substituent containing a halogen atom include halogen groups such as fluorine, chlorine, bromine and iodine, and halogen substitution having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. An alkyl group etc. can be mentioned. 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 number 1 to 20 such as a methoxycarbonyl group and an ethoxycarbonyl group. And an alkoxycarbonyl group. 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, 1- Methyl norbornene, 7-methyl norbornene, 5,5,6-trimethyl norbornene, 5-phenyl norbornene, 5-benzyl norbornene, 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-dimethano-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,
Examples thereof include 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, and 5-cyanonorbornene.

The cyclic olefin-based copolymer (a) is basically composed of the above-mentioned α-olefin component and cyclic olefin component, but within a range that does not impair the object of the present invention. In addition to the essential two components, other copolymerizable unsaturated monomer component may be contained, if necessary. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above α-olefin components, those not previously used, among the above cyclic olefin components, Something 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 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%.
On the other hand, it is preferable that [y] is 20 to 0.1 mol%, and particularly [x] is 82 to 99.5 mol%, and [y] is 18 to 0.5 mol%. 85-98 mol%
On the other hand, [y] is more preferably 15 to 2 mol%. Content rate [x] of α-olefin unit is 80 mol%
If it is less than 1, the glass transition temperature (Tg) of the copolymer and the tensile elastic modulus are increased, and the resulting copolymer composition and the elastic recovery of the film or sheet containing it as a main component and molding of the molded product. Impact resistance and elasticity of the product may become insufficient. On the other hand, when the content [y] of the cyclic olefin unit is less than 0.1 mol%, the crystallinity of the copolymer becomes high 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. It can be confirmed that the copolymer does not have a gel-like crosslinked structure by completely dissolving the copolymer in decalin at 135 ° C.

The glass transition temperature (Tg) of the cyclic olefin copolymer (a) must be 50 ° C. or lower. By using such a copolymer, it is possible to obtain a copolymer composition that can be suitably used at low temperature and a film, sheet, molded article or the like containing the copolymer composition as a main component. The preferred glass transition temperature (Tg) is -30.
It is -40 degreeC, More preferably, it is -30-35 degreeC. 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, and the intended use and the temperature used. The glass transition temperature (Tg) can be arbitrarily changed according to the above.

The cyclic olefin-based copolymer (a) is 13
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.01
It is preferably ˜20 dl / g. Intrinsic viscosity [η]
Is less than 0.01 dl / g, the strength may be remarkably reduced, and if more than 20 dl / g, the moldability may be significantly deteriorated. A more preferable intrinsic viscosity [η] is 0.
It is from 05 to 10 dl / g.

The cycloolefin copolymer (a) preferably has a crystallinity of 0 to 40% as measured by X-ray diffractometry. When the crystallinity exceeds 40%, elastic recovery and transparency may be deteriorated. A more preferable crystallinity is 0 to 30%, especially 0 to 25%.

The cyclic olefin copolymer (a) preferably has a tensile elastic 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 from the composition of the present invention, a large amount of energy is required at the time of packaging and a beautiful shape suitable for the shape of the packaged article is obtained. Packaging can be difficult. Further, when a molded product is formed, impact resistance may be insufficient. A more preferable tensile elastic modulus is 50 to 2,000 kg / cm ² .

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

The cyclic olefin copolymer (a) is a DS
Broad melting peak by C (temperature rise measurement) is 100 ° C
It is preferably less than. A copolymer having a sharp melting peak by DSC (temperature rise measurement) of 100 ° C. or higher has a wide composition distribution of the copolymer of cyclic oleophine and α-olefin, and the elastic recovery of the molded product is insufficient. May become. The broad melting peak by DSC (temperature rise measurement) is more preferably in the range of 10 to 95 ° C. In the DSC (temperature rise measurement), the melting point (melting peak) of the olefin-based copolymer cannot be seen sharply, and especially in the case of low crystallinity, it is almost impossible to measure at the ordinary polyethylene measurement condition level. There is no peak. Due to the characteristics of the thermal properties described above, the physical properties of the molded product can be obtained, and the molded product can be stably molded, for example, by widening the molding temperature range.

The cyclic olefin-based copolymer (a) may be a copolymer having only the physical properties in the above-mentioned range, and may partially include the copolymer having the physical properties outside the above-mentioned range. It may be In the latter case, all physical property values may be 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) are used.
Is efficiently produced by copolymerizing an α-olefin with a cyclic olefin by using a catalyst containing as the main component or a catalyst containing the following compounds (A), (B) and (C) as the main components. be able to. (A) Transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) Transition metal compound (A), or compound capable of forming an ionic complex from its derivative (C) Organoaluminum compound

In this case, the compound (A) may be any compound containing a transition metal selected from Group IVB of the periodic table, that is, titanium (Ti), zirconium (Zr) or hafnium (Hf). Compounds represented by the following general formula (I), (II) or (III) or derivatives thereof or compounds represented by the following general formula (IV) or derivatives thereof are particularly preferable. 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) [(I) to (IV), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group. , A substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R
¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an oxygen atom,
Halogen atom, C1-C20 alkyl group, C1
~ 20 alkoxy groups, C6-20 aryl groups,
Alkylaryl group or arylalkyl group, acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen It represents a ligand such as a molecule, a Lewis base, a chain unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon, and A represents a crosslink by a covalent bond. a, b, and c each represent an integer of 0 to 3, d and e each represent an integer of 0 to 2, f represents an integer of 0 to 6, and g, h, i, and j each represent an integer of 0 to 4. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When the 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. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. Specific examples of R ^{1 to} R ⁴ include, as halogen atoms, fluorine atom, chlorine atom, bromine atom, iodine atom;
A methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group,
2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; phenyl group, tolyl group as aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms Group, xylyl group, benzyl group; carbon number 1 to
20 as a heptadecyl carbonyloxy group as an acyloxy group; a trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: ethers such as dimethyl ether, diethyl ether, tetrahydrofuran as a Lewis base, 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 their derivatives; benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives as cyclic unsaturated hydrocarbons You can Examples of the covalent crosslink of A include methylene crosslink, dimethylmethylene crosslink, ethylene crosslink, dimethylsilylene crosslink, dimethylgermylene crosslink, and dimethylstannylene crosslink.

Examples of such compounds include the following and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound 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) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydrido zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

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

Examples of the 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, a hafnium compound, or a titanium compound having one or more of an alkyl group, an alkoxy group, and a halogen atom, such as a compound in which these zirconiums are replaced with hafnium or titanium, can be given. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetraphenoxyzirconium, tetra (2-ethylhexyloxy) zirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium , Bis (2,6-di-t-butylphenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy) dichlorozirconium, zirconium tetrakis (acetylacetonate),

Further, the compound (B) is not necessarily limited, but an ionic compound (B- which can form an ionic complex from the transition metal compound (A) or a derivative thereof.
1), specifically, a compound represented by the following formula (V) or (VI) can be preferably 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 ₃ C or R ¹¹ M ⁶ ) [(V), (VI) formula Wherein L ¹ is a Lewis base, M ³ and M ⁴
Are VB, VIB, VIIB, and VIII of the periodic table, respectively.
Group 5, IB, IIB, IIIA, IVA, and VA elements, M ⁵ and M ⁶ are IIIB of the periodic table, respectively.
Tribe, IVB, VB, VIB, VIIB, VIII, IA
Group, IB group, IIA group, IIB group and VIIA group, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms, respectively. , C1-20 alkyl group, C6-20 aryl group, alkylaryl group, arylalkyl group, C1-20 halogen-substituted hydrocarbon group, C1-20 acyloxy group, organic metalloid It represents a group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ⁸ and R ⁹ represent a cyclopentadienyl group and a substituted cyclopenta group, respectively. A dienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. m is an valence of M ³ and 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 ] have an ionic valence of 1 to 7 and p is 1.
The above integer, q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate.
Specific examples of M ³ and M ⁴ include B, Al, Si, P and A.
Specific examples of M ⁵ , such as s and Sb, include Li, Na, Ag,
Specific examples of Cu, Br, I, I _3, etc., M ⁶ include Mn, F
e, Co, Ni, Zn etc. can be mentioned. Z ¹ ~
Specific examples of Z ⁿ include, for example, a dialkylamino group such as a dimethylamino group and a diethylamino group;
As the alkoxy group of 20, methoxy group, ethoxy group, n
-Butoxy group; phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as aryloxy group having 6 to 20 carbon atoms; methyl group, ethyl group, n-propyl group, iso as alkyl group having 1 to 20 carbon atoms -Propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group; aryl group having 6 to 20 carbon atoms, alkylaryl group or phenyl group as arylalkyl group, p-tolyl group, benzyl group, 4-tertiary -Butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms -Fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-
Trifluorophenyl group, pentafluorophenyl group,
3,5-di (trifluoromethyl) phenyl group; F, Cl, Br, I as halogen atom; pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron as organic metalloid group A group can be mentioned. Specific examples of R ⁷ and R ¹⁰ are the same as those mentioned above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. be able to. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 4.

Among the compounds of the formulas (V) and (VI), M ³ ,
It is preferred that M ⁴ is boron. Of the compounds of formulas (V) and (VI), the following compounds can be used particularly preferably. Compound of formula (V) triphenylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenylphenylborate (N-Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate Triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, tetra ( Pentafluorophenyl) boric acid (tetraethylammonium), tetra (pentafluorophenyl) boric acid (methyltri (n-butyl) ammonium),
Tetra (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetra (pentafluorophenyl) borate methyldiphenylammonium, tetra (pentafluorophenyl) borate methyltriphenylammonium, tetra (pentafluorophenyl) borate dimethyldiphenylammonium , Anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate Dimethyl (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium),
Pyridinium tetra (pentafluorophenyl) borate,
Tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate ( O-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N)
-Benzylpyridinium), trimethylsulfonium tetra (pentafluorophenyl) borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, dimethyl tetra (3,5-ditrifluoromethylphenyl) borate Anilinium, triethylammonium hexafluoroarsenate,

Formula (VI) Compound Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate Decamethylferrocenium, tetra (pentafluorophenyl) acetylferrocenium borate, tetra (pentafluorophenyl)
Formylferrocenium borate, cyanoferrocenium tetra (pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) )
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate, and compounds other than those of formulas (V) and (VI), such as tri (pentafluorophenyl) boron,
Tri (3,5-di (trifluoromethyl) phenyl) boron, triphenylboron, etc. can also be used. Moreover, as the compound (B), an organic aluminum oxy compound (B-2) such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or chloro-containing alkylaluminoxane can be used. The degree of polymerization of this aluminoxane is 3 to 50, preferably 5 to 30.

Examples of the organoaluminum compound which is the component (C) include those represented by the following general formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 alkyl groups, alkenyl groups, aryl groups, arylalkyl groups, etc., Q is a hydrogen atom, Represents a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum Examples thereof include chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride.

The above-mentioned catalyst is the above-mentioned component (A) and component (B) [(B-1) or (B-2)] component, or the above-mentioned component (A), (B) [(B-1)]. The main component is the component and the component (C). In this case, the use conditions of the component (A) and the component (B-1) are not limited, but (A)
Component: (B-1) component ratio (molar ratio) 1: 0.01-
It is preferably 1: 100, particularly preferably 1: 1 to 1:10. The conditions for using the components (A) and (B-2) are as follows: component (A): component (B-2) (molar ratio as metal atom): 1:10 to 1: 10,000, particularly 1 : 20 ~
It is preferably 1: 5,000. The operating 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 used is usually 0 to 2, relative to 1 mol of the component (A).
It is 000 mol. When the component (C) is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the copolymer, which is not preferable. The components (A) and (B) may be contacted in advance and the contact product may be separated and washed before use, or they may be contacted within the polymerization system before use. Further, the component (C) is the component (A),
It may be used in contact with the component (B) or the contact product of the components (A) and (B). The contact may be made in advance or in the polymerization system.

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 250 ° C, particularly preferably -50 to 200 ° C. The ratio of the catalyst to the reaction raw material is 1 to 1 of raw material monomer / component (A) (molar ratio) or raw material monomer / component (B) (molar ratio).
It is preferably 0 ⁸ , particularly 100 to 10 ⁵ . Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is atmospheric pressure to
100 kg / cm ² G, preferably atmospheric pressure to 50 kg / c
m ² G. As a method for 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 used.

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, fats such as pentane, hexane, heptane and octane. Group hydrocarbons, halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

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

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

3. 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, and 0.02
-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 high,
Stable molding cannot be carried out, and if it exceeds 10 parts by weight, the transparency is lowered.

The type of anti-blocking agent is not particularly limited, and examples thereof include metal oxides, fluorides, nitrides, sulfates, phosphates, carbonates, and complex 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, nitriding Examples thereof include aluminum, calcium sulfate, strontium sulfate, barium sulfate, calcium phosphate, strontium phosphate, barium phosphate, calcium carbonate, strontium carbonate and barium carbonate.

The type of lubricant is not particularly limited, and one 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 optionally used. You can 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 preferably used.

The anti-blocking agent and the lubricant may be used alone or in combination.

In the cyclic olefin polymer composition of the present invention, if necessary, other additives such as antioxidants, stabilizers such as 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 device, a conventionally known one such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader or a continuous mixer can be used. A method of adding the additive to the masterbatch of the cyclic olefin copolymer can also be preferably adopted.

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

The olefin polymer composition of the present invention has transparency, elastic recovery, tackiness, puncture 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., so, for example, sealant film, pallet stretch film, commercial wrap film, agricultural film, meat packaging It can be used for various purposes such as films, shrink films, covering materials, damping materials, pipes, medical infusion packs, toys and the like. In particular, in the case of a film or sheet, it is excellent in elastic recovery, transparency and adhesiveness,
A film or sheet that hardly causes blocking and can be effectively used in various fields such as packaging, medical care, and agriculture can be obtained.

[0048]

EXAMPLES The present invention will be described in more detail below with reference to examples. Reference Example 1 (Copolymerization of ethylene and 2-norbornene) Under a nitrogen atmosphere, at room temperature, 15 liters of toluene, 23 mmols of triisobutylaluminum (TIBA), 38 mmoles of zirconium tetrachloride, and tetra (pentafluoro) were added to a 30 liters autoclave. Phenyl)
Add 60 micromoles of anilinium borate in this order,
Subsequently, 2.9 liters of a toluene solution containing 70% by weight of 2-norbornene (19 mol of 2-norbornene) 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 completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. The polymer is filtered off 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 resulting cyclic olefin copolymer (a
The physical properties of 1) were as follows. 30 of ¹³ C-NMR
The sum of the peaks due to ethylene and the peaks due to methylene at the 5th and 6th positions of norbornene appearing around ppm and 3
The norbornene content calculated from the ratio with the peak based on the methylene group at the 7-position of norbornene appearing 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 the X-ray diffraction method was 2.0%. Vibron 11-EA manufactured by Toyo Boulding Co., Ltd.
Using a mold, a measuring piece with a width of 4 mm, a length of 40 mm and a thickness of 0.1 mm was measured at a temperature rising 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, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) were calculated at 5 ° C. in terms of polyethylene, Mw was 62,300, Mn was 33,900, Mw /
It was Mn = 1.84. -50 at a temperature rising rate of 10 ° C./min by a 7 series DSC manufactured by Perkin Elmer.
When the melting point (Tm) was measured in the range of 150 ° C to 150 ° C,
Tm was 78 ° C. (broad peak).

Reference Example 2 (with ethylene and 2-norbornene
Copolymerization of Reference Example 1, the amount of zirconium tetrachloride used is 75
Micromol, the amount of anilinium tetra (pentafluorophenyl) borate used is 150 micromol, the amount of 2-norbornene used is 7.5 mol, and the ethylene partial pressure is 6 kg.
/ Cm ² and the polymerization temperature was 90 ° C, except that the cyclic olefin copolymer (a2) was obtained in the same manner as in Reference Example 1. The yield of the cyclic olefin-based copolymer (a2) was 2.66 kg. Polymerization activity is 389 kg /
It was gZr. Further, the norbornene content determined 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 above
To 100 parts by weight of the pellet of 1), 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 anti-blocking agent, and erucic acid amide as a lubricant. 0.2 parts by weight of
It was fed to a single-screw extruder having a diameter of 50 mm. Diameter 100m
m, extruded at 160 ° C from an annular die with a gap of 3 mm, and inflation-formed to a thickness of 20 μm, folding width of 3
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 measurement of physical properties such as tensile properties, elastic recovery properties, and optical properties of the obtained film.

Here, each item was measured as follows. Tensile elastic modulus: JIS-K7113 using autograph
According to. Tensile breaking strength: JIS-K711 using autograph
Followed by 3. Tensile breaking elongation: JIS-K711 using autograph
Followed by 3. Elastic recovery rate: Using an autograph, pulling speed 62 mm /
In a minute, a measuring piece having a width of 6 mm and a distance between the clamps of 50 mm (L ₀ ) is stretched by 150% and pulled, and after keeping the state for 5 minutes, it is contracted rapidly without being repelled, and after 1 minute, the sheet between the clamps is removed. The length (L ₁ ) was measured and determined by the following formula. Elastic recovery rate (%) = [1-{(L ₁ −L ₀ )}] × 10
0 In this case, good elastic recovery is 10% or more, especially 30%
Above all, above 60%. Haze: Digital Haze Computer (DIGITAL HA
ZE COMPUTER) (manufactured by Suga Test Instruments Co., Ltd.)
The measurement was performed according to S-K7105. Heat-sealing temperature: A test piece of 4 cm × 20 cm was heat-sealed with a width of 10 mm × 15 mm and a pressure of 2 kg / cm ²
After being pressure-bonded for 2 seconds and heat-sealed, it is left for 30 minutes, and the strength when peeled at a pulling speed of 200 mm / min is 300 g.
Was calculated as the temperature at which

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

Example 5 The cycloolefin copolymer (a obtained in Reference Example 1 above)
To 100 parts by weight of the pellet of 1), 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 anti-blocking agent, and erucic acid amide as a lubricant. 0.2 parts by weight of
Extruded from a T-die with a width of 500 mm and a gap of 1 mm at 190 ° C, and cast to form a thickness of 15 μm and a width of 400
m film was obtained. The discharge rate was 3 kg / hr, the pulling speed was 5 m / min, and the moldability was good. The results of measuring the physical properties of the obtained film are shown in Table 1.

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

[0056]

[Table 1]

[0057]

INDUSTRIAL APPLICABILITY According to the present invention, a cyclic olefin-based copolymer composition having excellent mechanical properties and elastic recoverability and excellent processability for forming a film or the like, and a film containing the composition as a main component or Sheets can be provided.

[Procedure amendment]

[Submission date] April 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

Examples of the organoaluminum compound which is the component (C) include those represented by the following general formula (VII) . ^{_{R 12 r AlQ 3-r ...}} (VII) (R 12 having 1 to 20 carbon atoms, preferably 1 to 12 alkyl group, an alkenyl group, an aryl group, a hydrocarbon group such as an aryl 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
It is in the range of. ) Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. Is.

Claims (3)

[Claims] 1. The following cyclic olefin copolymer (a) 1
00 parts by weight and cyclic olefin copolymer (b) 2
To 400 parts by weight of a cyclic olefin-based copolymer composition. (A): having a repeating unit derived from α-olefin and cyclic olefin and having a glass transition temperature (Tg) of 5
Cyclic olefin-based copolymer having a temperature of 0 ° C. or lower (b): having a repeating unit derived from α-olefin and a cyclic olefin, and having a glass transition temperature (Tg) of 5
The content of repeating units derived from a cyclic olefin at 0 ° C. or lower is 1 mol% or more than the content of repeating units derived from a cyclic olefin of the cyclic olefin copolymer of (a) above. Cyclic olefin copolymer having a large amount or a small amount of 1 mol% or more 2. The cyclic olefin-based copolymer (a)
100 parts by weight and cyclic olefin-based copolymer (b)
2 to 400 parts by weight, and 0.01 to 10 parts by weight of an anti-blocking agent and / or a lubricant are contained, The cyclic olefin type copolymer composition of Claim 1 characterized by the above-mentioned. 3. A film or sheet containing the cyclic olefin-based copolymer composition according to claim 1 or 2 as a main component.