JP3131250B2 - Olefin polymer composition and film or sheet comprising the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin having an appropriate elastic modulus and excellent elastic recovery and transparency, and is suitably used as a material for films and sheets in the fields of packaging, medicine, and agriculture. The present invention relates to a system polymer composition, and a packaging film or sheet comprising the composition.

[0002]

2. Description of the Related Art
Polyolefin resin films or sheets include polyethylene (PE), polypropylene (PP),
Polybutene, ethylene-propylene rubber (EPR),
There is a film or sheet obtained by extrusion or inflation molding of an ethylene-vinyl acetate copolymer (EVA) or the like, which is used as a packaging material, a tape, or the like. However, these polyolefin-based resin films or sheets have a drawback that they have an insufficient elastic recovery property, are easily sagged, and have a high modulus of elasticity, requiring a large amount of energy during packaging.

On the other hand, Japanese Patent Application Laid-Open No. 62-252406 discloses a random copolymer of an ethylene component and a specific cyclic olefin component. This copolymer is produced using a catalyst comprising a soluble vanadium compound and an organoaluminum compound, and has an ethylene content of 40 to 90 mol%, but has a high elastic modulus and extremely low elastic recovery. There's a problem. JP-A-61-211315 discloses a random copolymer of an ethylene component and a specific cyclic olefin component having an ethylene content of 90 to 98.
Mole% are disclosed. However, this copolymer is a copolymer having a glass transition temperature of at least 20 ° C. and less than 80 ° C., substantially at room temperature or higher, and its use as a soft resin is limited.

[0004] For this reason, development of a polyolefin-based resin excellent in the balance of physical properties such as elastic recovery and elastic modulus has been desired. The present invention has been made in view of the above circumstances, and has excellent elastic recovery, good transparency and an appropriate elastic modulus, and is effectively used as a material for films, sheets or various molded articles in various fields. An object is to provide an olefin polymer composition that can be used.

[0005]

In order to solve the above-mentioned conventional problems, the present applicant has already prepared a thin-walled molded product made of a norbornene-based copolymer having a good balance of physical properties obtained by copolymerizing a small amount of a cyclic olefin. Proposed (Japanese Patent Application No. 3-9)
9839). However, this norbornene-based copolymer has high tackiness, and has a problem in terms of molding stability when a film or sheet is formed by inflation molding or T-die molding. For this reason, the present inventors have further studied to provide a polyolefin-based resin which is particularly excellent in elastic recovery, has an appropriate elastic modulus, good transparency, and is excellent in balance of physical properties, and can be stably molded. Done. As a result, a specific cyclic olefin-based copolymer containing an α-olefin component represented by the formula [X] described below and a small amount of a cyclic olefin component represented by the formula [Y] satisfies the required characteristics; When an anti-blocking agent or a lubricant is blended with the cyclic olefin-based copolymer, or when an α-olefin-based polymer such as polyethylene is further blended, a composition is obtained in which tackiness is controlled and blocking is less likely to occur, Therefore, it has been found that the use of this composition has excellent elastic recovery properties, transparency and adhesiveness, and that a film or sheet can be formed stably, and the present invention has been accomplished.

Accordingly, the present invention provides an olefin polymer composition (first composition) comprising the following components (a) and (b), and an olefin polymer composition comprising the following components (a), (b) and (c): The polymer composition (the second composition) and the first
Alternatively, a packaging film or sheet comprising the second composition is provided. (A) a copolymer having a repeating unit represented by the following general formula [X] and a repeating unit represented by the following general formula [Y], having a glass transition temperature (Tg) of less than 30 ° C. 100 parts by weight of a cyclic olefin-based copolymer having a tensile modulus measured according to JIS-K7113 of less than 2,000 kg / cm ²

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

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms 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, and R ^{b to} R ^m may be the same or different from each other.) (B) Anti-blocking agent and And / or 0.01 to 5 parts by weight of a lubricant (c) 1 to 100 parts by weight of an α-olefin polymer

Hereinafter, the present invention will be described in more detail.
First, the cyclic olefin polymer of the component (a) will be described. In the repeating unit represented by the general formula [X], ^Ra is a hydrogen atom or a C1 to C1 as described above.
20 hydrocarbon groups are shown. Here, carbon number 1-2
Specific examples of the hydrocarbon group 0 include, for example, a methyl group,
Examples include an ethyl group, an isopropyl group, an isobutyl group, an n-butyl group, an n-hexyl group, an octyl group, and an octadecyl group. Specific examples of the α-olefin that provides a repeating unit 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.

In the 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, an oxygen atom or a nitrogen atom, as described above. Represents a substituent containing Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group,
An alkyl group having 1 to 20 carbon atoms such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group and the like, and a carbon number 6 such as phenyl group, tolyl group and benzyl group.
An alkylene group having 1 to 20 carbon atoms such as an aryl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, and a propylidene group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; Can be mentioned. ^{However, R b, R c, R} f, R g excluding an alkylidene group. When any one of R ^d , R ^e , and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen substituents such as fluorine, chlorine, bromine and iodine, and halogen substituents having 1 to 20 carbon atoms such as chloromethyl, bromomethyl and chloroethyl. 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 represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-
Trimethylnorbornene, 5-phenylnorbornene,
5-benzylnorbornene, 5-ethylidene norbornene, 5-vinylnorbornene, 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-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 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-1,4,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2,3-dichloro-1,1,
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-dimethylaminonorbornene, 5-cyanonorbornene and the like.

The cyclic olefin copolymer of the component (a) basically comprises the α-olefin component and the cyclic olefin component as described above, but within a range not to impair the object of the present invention. , In addition to these two essential components,
If necessary, other copolymerizable unsaturated monomer components may be contained. 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, Unused, cyclic dienes such as dicyclopentadiene and norbornadiene, butadiene, isoprene, 1,5-
Chain dienes such as hexadiene, cyclopentene,
And monocyclic olefins such as cycloheptene.

The cyclic olefin copolymer of the component (a) has a content of the repeating unit of the formula [X] derived from the α-olefin component and a formula [Y] derived from the cyclic olefin component.
The ratio of the content of the repeating unit ([X]: [Y]) is
It depends on the type and combination of α-olefin and cyclic olefin, and cannot be generally specified, but is usually 80 to 99.9 mol%: 20 to 0.1 mol%,
Preferably 82-99.5 mol%: 18-0.5 mol%, particularly preferably 85-98 mol%: 15-2 mol%
belongs to. When the repeating unit of the formula [X] is less than 80 mol%, the glass transition point and the tensile modulus of the copolymer are increased, and the elastic recovery of the composition of the present invention may be insufficient. on the other hand,
When the repeating unit of the formula [X] exceeds 99.9 mol%, the effect of introducing the cyclic olefin component may be insufficient.

The cyclic olefin copolymer of the component (a) is a substantially linear copolymer in which repeating units of the formula [X] and repeating units of the formula [Y] are arranged at random. It is preferable that it does not have a gel-like crosslinked structure. 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 of the component (a) preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.005 to 20 dl / g. If the intrinsic viscosity [η] is less than 0.005 dl / g, the strength of the composition of the present invention may decrease, and if it exceeds 20 dl / g, the moldability of the composition of the present invention may be deteriorated. More preferred intrinsic viscosity [η] is 0.05 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer of the component (a) is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2 , 00
000, especially 5,000 to 1,000,000, number average molecular weight Mn is 500 to 1,000,000, especially 2,000 to 800,000, and the molecular weight distribution (Mw
/ Mn) is preferably from 1.3 to 4, particularly preferably from 1.4 to 3. When the molecular weight distribution (Mw / Mn) is more than 4, the content of the low molecular weight compound increases, which may cause stickiness when the composition of the present invention is molded into a film or the like.

The glass transition temperature (Tg) of the cyclic olefin copolymer of the component (a) must be 30 ° C. or less. When such a copolymer is used, a film or sheet which can be suitably used even at a low temperature can be obtained. A more preferred glass transition temperature (Tg) is 20 ° C or lower, particularly 10 ° C or lower. The glass transition temperature (Tg) can be arbitrarily changed by changing the composition of the copolymer and the type of the monomer according to the intended use and required physical properties.

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

Further, the cyclic olefin copolymer of the component (a) has a broad melting peak at 90 ° C. by DSC.
Preferably it is less than. Copolymers whose DSC has a sharp melting peak at 90 ° C. or higher have insufficient randomness of arrangement of cyclic olefin and α-olefin and insufficient elastic recovery when molded into a film or the like. May be. In addition, the broad melting peak by DSC is more preferably in the range of 10 to 85 ° C. In the DSC measurement, the melting point (melting) peak of the cyclic olefin-based copolymer of the component (a) is not sharply observed. There is almost no peak.

The cyclic olefin copolymer of the component (a) preferably has a tensile modulus of less than 2,000 kg / cm ² as measured according to JIS-K7113. When the tensile elastic modulus is 2,000 kg / cm ² or more, when the composition of the present invention is used for a packaging film, a great amount of energy is required at the time of packaging, and beautiful packaging suitable for the shape of the article to be packaged is obtained. It can be difficult.
A more preferred tensile modulus is 50 to 1,500 kg / cm.
²

The cyclic olefin copolymer of the component (a) may be a copolymer consisting of only those having physical properties in the above-mentioned range, and some copolymers having physical properties out of the above-mentioned range may be used. It may be included. 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 of the component (a) is not limited, but the following compounds (A) and (B)
To produce efficiently by copolymerizing an α-olefin and a cyclic olefin using a catalyst containing as a main component or a catalyst containing the following compounds (A), (B) and (C) as main components. Can be. (A) a transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) a compound comprising a cation and an anion in which a plurality of groups are bonded to an element (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.

CpM¹R¹ _aR^Two _bR^Three _c … (I) Cp_TwoM¹R¹ _dR^Two _e ... (II) (Cp-A_f-Cp) M¹R¹ _dR^Two _e … (III) M¹R¹ _gR^Two _hR^Three _iR^Four _j … (IV) [wherein M represents (I) to (IV)¹ Is a Ti, Zr or Hf atom
And Cp is a cyclopentadienyl group, a substituted cyclope
Antadenyl, indenyl, substituted indenyl,
Trahydroindenyl group, substituted tetrahydroindenyl
A fluorenyl group or a substituted fluorenyl group. R
¹ , R^Two , R^ThreeAnd R^FourRepresents 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 or arylalkyl, carbon
Acyloxy group, allyl group, substituted allyl of formulas 1 to 20
Group, acetylacetonate group, substituted acetylacetonate
G, a substituent containing a silicon atom, or carbonyl,
Oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated hydrocarbon
Or a ligand such as a cyclic unsaturated hydrocarbon, and A is a covalent bond.
Shows cross-linking due to bonding. a, b and c are each 0 to 3
Integers, d and e are each an integer of 0 to 2, and f is 0 to 6
Integers, g, h, i and j each represent an integer of 0 to 4
You. R¹ , R^Two , R ^ThreeAnd R^FourIs two or more
To form a ring. The above Cp has a substituent
The substituent is an alkyl group having 1 to 20 carbon atoms
Is preferred. In the formulas (II) and (III), two
Cp may be the same or different from each other.
There may be. ]

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
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. 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; a methyl group, an ethyl group, an n-propyl group and an iso group as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as an alkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; A phenyl group as an alkylaryl group or an arylalkyl group,
Tolyl group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, tetrahydrofuran as a Lewis base Ethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N,
Amines such as N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline and the like; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene; 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslink by the covalent bond of A include methylene crosslink, dimethylmethylene crosslink, ethylene crosslink, dimethylsilylene crosslink,
Examples include dimethylgermylene crosslinks and dimethylstannylene crosslinks.

Examples of such compounds include the following 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 the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (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,

The above general formulas (I), (II) and (III)
Compounds other than the cyclopentadienyl compound represented by the formula do not impair the effect. Examples of such compounds include compounds of formula (IV) above, for example, alkyl groups such as tetrabenzyl zirconium, bis (2,5-di-t-butylphenoxy) dimethyl zirconium and / or
Alternatively, a titanium compound, a zirconium compound, or a hafnium compound having an alkoxy group may be used.

The compound (B) is not particularly limited, but a compound 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-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, Sb
Etc., Li Specific examples of ^{M 5, Na, Ag, Cu} , B
r, I, I _3, etc., Mn Specific examples of M ^6, Fe, C
o, 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;
A phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as an aryloxy group having 6 to 20 carbon atoms; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group as an alkyl group having 1 to 20 carbon atoms; n-butyl group, n-octyl group, 2-ethylhexyl group; phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group as an aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms , 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-di (trifluoromethyl) phenyl group; F, Cl, Br, I as a halogen atom; pentamethylantimony group, trimethylsilyl group, trimethyl gel as an organic metalloid group Examples include a mill group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. R ⁷ , R ¹⁰
Specific examples include the same as those described 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. Can be
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, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (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) borate (tetraethylammonium), tetra (pentafluorophenyl) borate (methyltri (n-butyl) ammonium),
Tetra (pentafluorophenyl) borate (benzyl tri (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, dimethyl tetra (pentafluorophenyl) borate (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,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate Decamethylferrocenium, acetylferrocenium tetra (pentafluorophenyl) 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) borate (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) borate (zinc tetraphenylporphyrin) tetrafluoroborate, Silver hexafluoroarsenate, silver hexafluoroantimonate, and compounds other than formulas (V) and (VI), such as tri (pentafluorophenyl) boron and tri (3,5-di (trifluoromethyl) phenyl) boron , Triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include compounds 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 carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; 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.) More specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum Chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

[0034]

Embedded image A chain aluminoxane represented by the formula: (R ¹² is of the formula (VII)
Indicates the same as s represents the degree of polymerization, usually 3 to 50.
It is. )

[0035]

Embedded image A cyclic alkylaluminoxane having a repeating unit represented by the formula: (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3
~ 50. ) Among the compounds of the formulas (VII) to (IX), preference is given to the compounds of the formula (VII), particularly preferred (VII)
Compounds of the formula wherein r = 3, among which are trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum.

The method for producing the aluminoxane includes a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The above-mentioned catalyst comprises the above-mentioned component (A) and (B)
Component or component (A), component (B) and component (C) as main components. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.01 to 1: 1.
00, particularly preferably 1: 1 to 1:10. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.
The amount of the component (C) is usually 0 to 2,000 mol per 1 mol of the component (A). 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
It may be used in contact with the component (A), the component (B) or the contact product of the component (A) and the component (B). Contact is
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, 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, 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 combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

In the present invention, the type of the anti-blocking agent used as the component (b) is not particularly limited, and examples thereof include metal oxides, fluorides, nitrides, sulfates, phosphates, carbonates, and composite salts thereof. And the like. 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 used as the component (b) is not 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 are optionally used. be able to. As a lubricant, specifically, liquid paraffin,
Natural paraffin, polyethylene wax, fluorocarbon oil, lauric acid, palmitic acid, stearic acid, iristearic acid, hydroxylauric acid, hydroxystearic acid, oleamide, lauric amide, erucamide, methyl stearate, butyl stearate, Stearyl alcohol, cetyl alcohol, isocetyl alcohol, ethylene glycol, diethylene glycol, fatty acid monoglyceride and the like can be suitably used. In addition, only one of the anti-blocking agent and the lubricant may be used, or both may be used in combination.

In the present invention, at least the following general formula CH ₂ ＣＨCHR ¹³ (wherein R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) as the α-olefin polymer of the component (c). )), A homopolymer or a copolymer containing one component of the α-olefin represented by the above-mentioned component (a). Specifically, polyethylene, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / acetic acid Vinyl copolymer, ethylene / acrylic acid copolymer and its metal salt, polypropylene, propylene / ethylene copolymer, propylene / 1-butene copolymer, poly-1-butene, 1-butene / ethylene copolymer, 1 -Butene-propylene copolymer, 1-butene-4-methyl-1
-Pentene copolymer, poly 4-methyl-1-pentene,
Poly-3-methyl-1-butene and the like. Particularly preferred among these are polyethylene and ethylene / 1-
Butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer and the like.

The first composition of the present invention comprises the component (b) based on 100 parts by weight of the cyclic olefin copolymer of the component (a).
In an amount of 0.01 to 5 parts by weight. In the second composition of the present invention, the antiblocking agent and / or the lubricant of the component (b) are blended in the same amount as the first composition with respect to 100 parts by weight of the cyclic olefin copolymer of the component (a). Further, 1 to 100 parts by weight, preferably 2 to 80 parts by weight, particularly preferably 3 to 50 parts by weight of the α-olefin polymer of the component (c) is blended. The second composition has the effect of reducing the amount of the component (b) and reducing the occurrence of problems such as bleed-out by blending the α-olefin-based polymer of the component (c). In the first and second compositions, if the amount of the component (b) is less than 0.01 part by weight, the adhesiveness becomes too large and molding becomes difficult. If the amount exceeds 5 parts by weight, the transparency becomes low. descend. When the amount of the component (c) is less than 1 part by weight in the second composition, there is no effect of mixing the α-olefin polymer, and
If the amount is more than 10 parts by weight, the elastic recovery becomes insufficient.

The 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 inorganic additives. Organic fillers, dyes, pigments and the like may be added.

The production method of the olefin polymer composition of the present invention is not 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 in which an additive is added to a master batch made of a cyclic olefin copolymer or an α-olefin resin can also be preferably used.

The olefin polymer composition of the present invention can be formed into films, sheets, and various molded products 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 used as a packaging film or sheet, it is excellent in elastic recovery, transparency, and adhesiveness, hardly causes blocking, and can be effectively used in various fields such as packaging, medical care, and agriculture. A film or sheet can be obtained.

[0047]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. Reference Example 1 (1) Preparation of ferrocenium tetra (pentafluorophenyl) borate 20 mmol of ferrocene (Cp ₂ Fe) and concentrated sulfuric acid 40
and 1 ml at room temperature to give a dark blue solution. This solution was poured into 1 liter of water and stirred, and the resulting deep blue aqueous solution was added to 500 ml of an aqueous solution of 20 mmol of lithium tetra (pentafluorophenyl) borate. The precipitated pale blue solid was collected by filtration, washed five times with 500 ml of water, and dried under reduced pressure to obtain ferrocenium tetra (pentafluorophenyl) borate ([Cp ₂ Fe] [B (C ₆ F ₅ ) ₄ ]), 17 mmol.

(2) Copolymerization of ethylene and 2-norbornene In a 30 liter autoclave at room temperature under a nitrogen atmosphere, 15 liters of toluene, 23 mmoles of triisobutylaluminum (TIBA), 0.11 mmoles of biscyclopentadienyl zirconium dichloride were added. 0.15 mmol of ferrocenium tetra (pentafluorophenyl) borate prepared in (1) above was added in this order,
Subsequently, 2.25 liter of a toluene solution containing 70% by weight of 2-norbornene (15.
(0 mol), and the mixture was heated to 90 ° C. and reacted for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ² . After completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate a polymer, and the polymer was collected by filtration and dried to obtain a cyclic olefin-based copolymer (a1). The yield of the cyclic olefin copolymer (a1) was 3.48 kg. The polymerization activity was 347 Kg / gZr.

The obtained cyclic olefin copolymer (a
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of the peak based on ethylene and the peak based on methylene at the 5- and 6-positions of norbornene, which appears around 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 9.2 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.99 dl / g, and the crystallinity determined by X-ray diffraction was 1.0%. Using a piperon 11-EA type manufactured by Toyo Boulding Co., Ltd., a measuring 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. The glass transition temperature (Tg) was determined from the peak of the loss modulus of elasticity (E ″) of the sample, and the Tg was 3 ° C. ALC / OPC150C manufactured by Waters, Inc. was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. 135 ° C
The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene.
Mw is 54,200, Mn is 28,500, Mw / Mn
Was 1.91. Using a Perkin-Elmer 7 series DSC at a rate of 10 ° C./min, -50 ° C.
When the melting point (Tm) was measured in the range of 150 ° C., the Tm
Was 73 ° C. (broad peak).

Example 1 The cyclic olefin copolymer (a) obtained in Reference Example 1 was used.
1.05 parts by weight of diatomaceous earth as an anti-blocking agent, 0.25 parts by weight of erucamide as a lubricant, and L-LDPE as an α-olefin polymer (Idemitsu Petrochemical Co.) 0438N, MI =
4 g / 10 min, D = 0.920 g / cm ³ )
Parts by weight were mixed and supplied to a 50 mm diameter single screw extruder.
160 mm from an annular die with a diameter of 100 mm and a gap of 3 mm
Extruded at ℃, thickness 20μ by inflation molding
m, a film having a folded width of 340 mm was obtained. The discharge amount is 7kg
/ Hr, the tensile speed was 6.0 m / min. The moldability was good. Table 2 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 maintained 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 ) / L ₀ }] ×
100 In this case, a good elastic recovery rate is 10% or more, especially 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 IS-K7105. Heat seal temperature: A test piece of 4 cm × 20 cm was heat-sealed at a heat seal 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. The above measuring methods are all the same in the following examples.

Reference Example 2 Reference Example 1 was repeated except that the amount of biscyclopentadienyl zirconium dichloride was changed to 0.075 mmol and the amount of 2-norbornene was changed to 7.5 mol in (2) of Reference Example 1. In the same manner as in the above, a cyclic olefin-based copolymer (a2) was obtained. The yield of the cyclic olefin copolymer (a2) was 2.93 kg, and the polymerization activity was 428 kg / gZr. The norbornene content obtained in the same manner as in Reference Example 1 was 4.9 mol%, and the intrinsic viscosity [η] was 1.22 dl.
/ G, glass transition temperature (Tg) is -7 ° C, Mw is 72,
400, Mn is 36,400, Mw / Mn is 1.99,
Melting point (Tm) was 84 ° C. (broad peak).

Examples 2 to 7 and Comparative Example 1 The procedure of Example 1 was repeated except that the types and amounts of the components were changed as shown in Table 1. Table 1 shows the results of the physical property measurement. Reference Example 3 The copolymer obtained in (2) of Reference Example 1 was heated at 190 ° C.
Hot pressing was performed at 0 kg / cm ² to obtain a sheet having a thickness of 100 μm. Table 1 shows the results of the physical property measurement.

[0054]

[Table 1]

[0055]

As described above, according to the olefin polymer composition of the present invention, a film or sheet having excellent elastic recovery, transparency and tackiness, such as a film or sheet for packaging, can be stabilized. Can be molded into

────────────────────────────────────────────────── (5) References JP-A-3-188145 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 23/00-23/36 C08J 5 / 18

Claims (3)

(57) [Claims] (A) The following general formula [X] (In the formula [X], Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) And a general unit represented by the following general formula [Y]: (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms 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, and R ^{b to} R ^m may be the same or different from each other.) A copolymer having a glass transition temperature (Tg) of 30 ° C. or less and a tensile modulus of 2,000 Kg / cm measured in accordance with JIS-K7113.
An olefin polymer composition comprising: 100 parts by weight of a cyclic olefin copolymer having a value of less than ² ; and (b) 0.01 to 5 parts by weight of an antiblocking agent and / or a lubricant. 2. (a) 100 parts by weight of the cyclic olefin-based copolymer according to claim 1, (b) 0.01 to 5 parts by weight of an anti-blocking agent and / or a lubricant, and (c) an α-olefin-based copolymer. An olefin-based polymer composition comprising 1 to 100 parts by weight of a polymer. 3. A packaging film or sheet comprising the olefin polymer composition according to claim 1 or 2.