JP3213049B2 - Sheet or film composed of α-olefin copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet or film made of a polyolefin copolymer having a good balance of physical properties such as an excellent elastic recovery and an appropriate elastic modulus. , A vibration-proof material, a medical film or sheet, a transparent conductive film or sheet, a moisture-proof film or sheet, an adhesive film or sheet, a stretchable film or sheet, a sealant or an agricultural film.

[0002]

2. Description of the Related Art
Examples of the polyolefin-based film or sheet include a film or sheet obtained by extruding polyethylene (PE), polypropylene (PP), polybutene or ethylene-propylene rubber (EPR), ethylene-vinyl acetate copolymer (EVA), and the like. It is being studied as a material and tape for use. However, these have a drawback that they have insufficient elastic recovery properties, are easily sagged, and have a high modulus of elasticity, requiring a large amount of energy during packaging.

Further, Japanese Patent Application Laid-Open Nos. 2-180976, 2-196632, 2-289637
In the publications, sheets and films comprising a cyclic olefin-based copolymer are disclosed, but the copolymer used here has a high glass transition temperature of 50 to 230 ° C., and the obtained sheet or film Has high rigidity and extremely low elastic recovery. Therefore, development of a polyolefin-based film or sheet excellent in balance of physical properties, such as being excellent in elastic recovery property and having an appropriate elastic modulus, is desired.

[0004]

Means for Solving the Problems The present inventors have intensively studied to solve these conventional problems. as a result,
It has been found that the above object is achieved when an α-olefin copolymer having a specific structure having a specific glass transition temperature (Tg) is used as a sheet forming material, and based on this finding, the present invention has been completed. It has arrived. That is, the present invention provides an α-olefin component having a repeating unit represented by the general formula [I] , a monocyclic olefin, a substituted monocyclic cyclic
Olefin and repeating unit represented by general formula [II]
A sheet obtained by copolymerizing a cyclic olefin component selected from the group consisting of cyclic olefins having a glass transition temperature (Tg) of 30 ° C. or lower. Or provide a film.

The α-olefin copolymer used in the present invention has a low Tg and exhibits excellent elastic recovery in a normal temperature range (room temperature). The α-olefin copolymer used in the present invention is easy to mold and contains no unsaturated bond, so that it has excellent weather resistance and good transparency.

Hereinafter, the present invention will be described in more detail.
The sheet or film of the present invention is represented by the general formula [I].
And α-olefin component having a repeating unit, mono-
Cyclic olefin, substituted monocyclic cyclic olefin and general formula
Cyclic olefin having a repeating unit represented by [II]
It is composed of an α-olefin-based copolymer obtained by copolymerizing a cyclic olefin component selected from the group consisting of: a repeating unit derived from an α-olefin, and a repeating unit derived from a cyclic olefin. It is composed of an α-olefin copolymer. Where α
-As the olefin component , the following general formula [I]

Embedded image What has a repeating unit represented by these is used . In the repeating unit represented by the general formula [I], R ¹
Represents a hydrogen atom .

Further, the cyclic olefin component includes a monocyclic cyclic olefin, a substituted monocyclic cyclic olefin, and a compound represented by the following general formula [II]:

Embedded image Those selected from the group consisting of cyclic olefins having a repeating unit represented in is used.

The monocyclic olefin which forms one of the cyclic olefin components includes, for example, cyclobutene, cyclopentene, cyclohexene and the like. Also,
Examples of the substituted monocyclic olefin constituting one of the cyclic olefin components include 3-methylcyclopentene and 3-methylcyclohexene.

Further, one of the cyclic olefin components is a cyclic olefin having a repeating unit represented by the above general formula [II].
^{2 to} R ¹³ 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 0 or 1 . Note that R ¹⁰ or R ¹¹ and R ¹² or R ¹³ may form a ring with each other. Further, R ^{2 to} R ¹³ may be the same or different from each other.

Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as an alkylidene group having 1 to 20 carbon atoms, a vinyl group and an allyl group. However, R in the general formula [II]
² , R ³ , R ⁶ and R ⁷ exclude an alkylidene group. Note that R
^{When any of 4} , R ⁵ , R ^{8 to} R ¹³ 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. Further, specific examples of the substituent containing an oxygen atom include a methoxy group, an ethoxy group,
Examples thereof include an alkoxy group having 1 to 20 carbon atoms such as a propoxy group and a phenoxy group, and an alkoxycarbonyl group having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. Further, 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 cyclic olefin having a repeating unit represented by the general formula (II) 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-ethylidenenorbornene, 5-vinylnorbornene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5
-Fluoronorbornene, 5,5,6-trifluoro-
6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-
Norbornene or its derivatives such as dicarboxyl norbornene anhydrate, 5-dimethylaminonorbornene and 5-cyanonorbornene;
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2-methyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2-ethyl-1,4,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-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-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 1,5-
Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene and the like can be mentioned. Among these, it is preferable to use the above-mentioned norbornene or a derivative thereof as the cyclic olefin component.

The α-olefin copolymer used in the present invention is basically obtained by copolymerizing an α-olefin component and a cyclic olefin component as described above.
As long as the object of the present invention is not impaired, other copolymerizable unsaturated monomer components may be used, if necessary, in addition to these two essential components. As such an unsaturated monomer which may be optionally copolymerized, specifically, the above-mentioned α
Olefin components not previously used,
Among the above-mentioned cyclic olefin components, those not previously used, cyclic dienes such as dicyclopentadiene and norbornadiene, butadiene, isoprene, 1,1,
Chain dienes such as 5-hexadiene are exemplified.

Further, the α-olefin-based copolymer of the present invention needs to have a glass transition temperature (Tg) of 30 ° C. or less. Use of such a copolymer shows excellent elastic recovery at room temperature. A more preferred glass transition temperature (Tg) is -30 to 25C, particularly -30 to 20C. In this case, the α-olefin copolymer used in the present invention depends on the intended use, the temperature used, and the like.
The glass transition temperature (Tg) can be arbitrarily controlled by changing the type and composition of the monomer.

Further, the α-olefin-based copolymer is
It is preferable that the melting point by SC is 90 ° C. or less, particularly 10 to 85 ° C., especially 20 to 80 ° C., or one which does not show a clear melting point. A copolymer having a sharp melting peak exceeding 90 ° C. by DSC has insufficient homogeneity of copolymerization of the α-olefin component and the cyclic olefin component, and has a sufficient elastic recovery when formed into a sheet or film. And transparency may not be obtained. In the DSC measurement, the melting point (melting peak) of the α-olefin-based copolymer used in the present invention is not seen sharply, and especially in the case of the one having a low crystallinity, it is almost impossible to measure at the level of ordinary polyethylene measurement conditions. No peak.

In the α-olefin copolymer used in the present invention, the content of the repeating unit derived from the α-olefin component [x] and the content of the repeating unit derived from the cyclic olefin component [y] are determined. Ratio ([x]:
[Y]) varies depending on the type and combination of the α-olefin component and the cyclic olefin component, and cannot be generally specified, but is usually 82 to 99.9 mol%: 18 to 0.1 mol%. , Preferably 85 to 99.5 mol%: 15 to 0.5 mol%, particularly preferably 90 to 98 mol%.
Mol%: 10 to 2 mol%. When the content [y] of the repeating unit derived from the cyclic olefin component exceeds 18 mol%, Tg may be higher than 30 ° C., resulting in high rigidity and insufficient elastic recovery. Would. On the other hand, if it is less than 0.1 mol%, the copolymer becomes crystalline, and the elastic recovery and transparency may be reduced.

The α-olefin copolymer is a substantially linear copolymer in which repeating units derived from an α-olefin component and repeating units derived from a cyclic olefin component are randomly arranged, 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 completely dissolving the copolymer in decalin at 135 ° C.

Further, the α-olefin copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is preferably 0.01 to 20 dl / g. If the intrinsic viscosity [η] is less than 0.01 dl / g, the mechanical strength of the sheet or film may decrease, while if it exceeds 20 dl / g, the moldability to the sheet or film may deteriorate. There is. More preferred intrinsic viscosity [η] is 0.05 to 10 dl / g.

The molecular weight of the α-olefin copolymer of the present invention is not particularly limited, but the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 1,000 to 2,000,000, Especially 5,000 to 1,000,000, number average molecular weight (Mn) is 500 to
1,000,000, in particular 2, 000 ～800,000, molecular weight distribution (Mw / Mn) 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 substance increases, which may cause the surface to become sticky when formed into a sheet or film.

The α-olefin copolymer of the present invention preferably has a crystallinity of 0 to 40% as measured by X-ray diffraction. When the crystallinity exceeds 40%, the transparency is lowered, and the elastic recovery may be lowered. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.
Further, in the α-olefin copolymer of the present invention, the elastic recovery after 150% tension is preferably 10% or more, more preferably 30%, in the measurement of the elastic recovery shown by the following equation. Above, particularly preferably 60% or more. If the elastic recovery is less than 10%, for example, when the article is wrapped with a film, the article tends to be sagged.

(Equation 1)

The α-olefin copolymer used in the present invention preferably has a tensile modulus of not more than 3,000 kg / cm ² . If the tensile modulus exceeds 3,000 kg / cm ² ,
When used as a sheet or film, the flexibility may be insufficient. More preferred tensile modulus is 50 to
2,000kg / cm ^2, is particularly 100 ~1,500kg / cm ^2.

The α-olefin copolymer used in the present invention may be a copolymer consisting of only those having the above-mentioned physical properties. In this case, the glass transition temperature (Tg) is 30 ° C. The following may be a mixture of copolymers having different Tg. Further, in the present invention, a copolymer partially having a physical property out of the above range may be contained. In the latter case, it is sufficient that the entire physical property value is included in the above range.

Next, the method for producing the α-olefin copolymer used in the present invention is not particularly limited. For example, the α-olefin copolymer can be produced efficiently by the following method. In other words, in addition to the catalyst containing (A) the transition metal compound and (B) a compound which reacts with the transition metal compound to form an ionic complex, as a main component, or in addition to the components (A) and (B), Further, (C) copolymerization of the α-olefin component and the cyclic olefin component as described above using a catalyst containing an organoaluminum compound as a main component,
The α-olefin-based copolymer used in the present invention can be produced efficiently.

Here, the transition metal compound component (A) of the catalyst includes groups IVB, VB, VIB, VIIB of the periodic table.
Transition metal compounds containing transition metals belonging to Group VIII and Group VIII can be used. As the transition metal, specifically, titanium, zirconium, hafnium, chromium,
Manganese, nickel, palladium, platinum and the like are preferable,
Among them, zirconium, hafnium, titanium, nickel,
Palladium is preferred.

As such a transition metal compound (A), various compounds can be mentioned. In particular, compounds containing a transition metal of Group IVB and Group VIII, especially a transition metal selected from Group IVB of the periodic table, ie, titanium A compound containing (Ti), zirconium (Zr) or hafnium (Hf) can be suitably used. Among them, in particular, a cyclopentadienyl compound represented by the following general formula [III], [IV] or [V] or a derivative thereof, or a compound represented by the following general formula [VI] or a derivative thereof It is suitable.

That is, the general formula [III] is as follows.

Embedded image ^{_{CpM 1 R 14 a R 15 b}} R 16 c ...... (III) In general formula [IV] are as follows.

Embedded image Cp ₂ M ¹ R ¹⁴ _a R ¹⁵ _b ... [IV] Further, the general formula [V] is as follows.

(Cp-Ae-Cp) M ¹ R ¹⁴ _a R ¹⁵ _b ... [V] Next, the general formula [VI] is as follows.

Embedded image M ¹ R ¹⁴ _a R ¹⁵ _b R ¹⁶ _c R ¹⁷ _d ... [VI]

In the above formulas [III] to [VI], M ¹
Is a transition metal selected from group IVB of the periodic table, ie, T
i, Zr or Hf atom is shown. Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group,
A cyclic unsaturated hydrocarbon group such as an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group, or a chain unsaturated hydrocarbon group. Further, R
¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a ligand such as a σ-binding ligand, a chelating ligand or a Lewis base, and specific examples of the σ-binding ligand include specific ligands. A hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
Aryl group, alkylaryl group or arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, etc., and the chelating ligand is acetyl. Examples thereof include an acetonate group and a substituted acetylacetonate group.
A represents a covalent crosslink. Here, a, b, c and d each represent an integer of 0 to 4, and e represents an integer of 0 to 6. Two or more of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring. When the Cp has a substituent, the substituent has 1 to 20 carbon atoms.
Are preferred. Further, in the formulas [IV] and [V], two Cp's may be the same or different from each other.

The substituted cyclopentadienyl group in the above formulas [III] to [V] includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2, -Dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadi An enyl group,
Pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like.

Next, R in the above formulas [III] to [VI]
Examples of ¹⁴ to R ^17, for example, a fluorine atom as a halogen atom, a chlorine atom, a bromine atom, an iodine atom;
As an alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group, a 2-ethylhexyl group;
A methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as the alkoxy group having 0;
A phenyl group, a tolyl group, a xylyl group, a benzyl group as an aryl group, an alkylaryl group or an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group as a substituent containing a silicon atom; (Trimethylsilyl) methyl group: Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine,
Amines such as tributylamine, N, N-dimethylaniline, pyridine, 2,2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene and 1-pentene , Isoprene, pentadiene, 1-hexene and derivatives thereof; and cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof.

Examples of the crosslink by a covalent bond of A in the above formula [V] include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a 1,1'-cyclohexylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethyl crosslink. Stannylene crosslinking and the like can be mentioned.

Examples of such compounds include the following zirconium compounds and zirconium of these compounds:
Compounds substituted with titanium or hafnium are mentioned. That is, as an example of such a compound, for example, a zirconium compound, first, as the compound of the above formula [III], (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium , (Pentamethylcyclopentadienyl) tribenzyl zirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) ) Triphenyl zirconium, (cyclopentadienyl) tribenzyl zirconium, (cyclopentadienyl) trichloro zirconium, (cyclopentadienyl) trimethoxy zirconium, (cyclo (Pentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (Methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl ) Trichlorozirconium and the like.

As an example of such a compound, for example, a zirconium compound, the compounds of the above formula [IV] include bis (cyclopentadienyl) dimethylzirconium and bis (cyclopentadienyl) diphenylzirconium. , Bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) di Zirconium hydride, bis (cyclopentadienyl)
Monochloromonohydride zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium , Bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclopentadienyl) hydridomethyl Zirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium, and the like.

Further, taking a zirconium compound as an example of such a compound, first, as the compound of the above formula [V], ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis ( Tetrahydroindenyl)
Dimethyl zirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethyl zirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexylidene (9-fluorenyl) ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium and the like.

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas [III], [IV] and [V] include the compounds of the above formula [VI]. An alkyl group such as a compound in which zirconium is replaced with hafnium or titanium,
Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkoxy group and a halogen atom.

That is, taking a zirconium compound as an example of the compound of the formula [VI], tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy Trichlorozirconium, dibutoxydichlorozirconium, bis (2,5-
Di-t-butylphenoxy) dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate) and the like.

The transition metal other than the above-mentioned transition metals other than Group IVB, that is, a transition metal compound containing a transition metal of Groups VB to VIII is not particularly limited, and examples thereof include the following compounds. First, specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydridecarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium , Bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like.

Further, specific examples of the manganese compound include, for example, tricarbonyl (cyclopentadienyl)
Manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like can be mentioned.

As a specific example of the nickel compound,
For example, dicarbonylbis (triphenylphosphine)
Nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), chlorohydridobis (tricyclohexylphosphinenickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) Nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allylnickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel _{chloride, (C 6 H 5) Ni} {OC (C 6 H 5) CH = P (C
_{6 H 5) 2} {P} (C 6 H 5) 3}, (C 6 H 5) Ni {OC (C 6 H 5) C
(SO ₃ Na) = P (C ₆ H ₅ ) ₂ {P (C ₆ H ₅ ) ₃ }.

Further, specific examples of the palladium compound include, for example, dichlorobis (benzonitrile palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, palladium bis ( Acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5-cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl)
Palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonato) (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, etc. No.

Next, as the compound component (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. And a compound comprising an anion in which a plurality of groups are bonded to an element, particularly a coordination complex compound comprising a cation and an anion in which a plurality of groups are bonded to an element. As a compound comprising such a cation and an anion having a plurality of groups bonded to an element, a compound represented by the following formula [VII] or [VIII] can be suitably used.

That is, the general formula [VII]

([L ¹ -R ¹⁸ ] ^{k +} ) _p ([M ² Z ¹ Z ²
... ^{Z n] _{(n-m) -) q}} ...... [VII] or formula [VIII]

Embedded image ^{([L 2] k} _{+) p} ^{([M 3 Z 1 Z 2 ... Z} n ] ^{_(n-m) -)} a _q ...... represented by [VIII] compound can be suitably used.

In the above formulas [VII] and [VIII], L ¹ is a Lewis base, and M ² and M ³ are groups VB, VIB, VIIB and VIII of the periodic table, respectively. , I
It is an element selected from Group B, IIB, IIIA, IVA and VA, and preferably an element selected from IIIA, IVA and VA. However, L ² is M ⁴ , R ¹⁹ R
²⁰ M ⁵ , (R ²¹ ) ₃ C or R ²² M ⁵ . Further, M ⁴ and M ⁵ are groups IIIB of the periodic table,
IVB, VB, VIB, VIIB, VIII, IA,
It is an element selected from the group IB, IIA, IIB and VIIA. ^Further, 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, carbon atoms 6-20 An aryl group, 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 group or a halogen atom. Z ^{1 to} Z
Two or more of ⁿ may combine with each other to form a ring. Next, R ¹⁸ 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. R ¹⁹ and R ²⁰ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ²¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group. Or an arylalkyl group. R ²² represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. Further, m is a valence of M ² or M ³ and represents an integer of 1 to 7, and n is 2 to 8
Indicates an integer. K is [L ¹ -R ¹⁸ ], [L ² ]
Represents an integer of 1 to 7, and p is an integer of 1 or more, and q is (p × k) / (nm).

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Also,
Specific examples of M ² and M ³ include B, Al, Si, P,
As, Sb and the like are mentioned, and B or P is preferable.
Further, specific examples of ^{M 4} is, Li, Na, Ag, C
u, Br, I, _{I 3} and the like, and specific examples of ^{M 5} are, Mn, Fe, Co, Ni, Zn and the like.

[0044] ^Z 1 Specific examples of the to Z ^n, for example, dimethylamino group as a dialkylamino group, a diethylamino group, a methoxy group as an alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group, a carbon number 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group, aryl group having 6 to 20 carbon atoms,
A phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group, p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, F, Cl, Br,
I, an acetoxy group, a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms, a pentamethylantimony group, a trimethylsilyl group as an organic metalloid group,
Examples include a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group.

Specific examples of R ¹⁸ and R ²¹ are the same as those described above. Specific examples of the substituted cyclopentadienyl group of R ¹⁹ and R ²⁰ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Is mentioned. 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 5. Among the compounds represented by the formulas [VII] and [VIII], M ² ,
Those in which M ³ is boron are preferred.

As the component (B) used in the present invention, among the compounds represented by the general formula [VII] or the general formula [VIII], specifically, the following are particularly preferably used. be able to. First, the general formula [VII]
Examples of the compound represented by are, for example, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, Benzyl benzyl tri (n-butyl) ammonium, dimethyl diphenyl ammonium tetraphenyl borate, methyl triphenyl ammonium tetraphenyl borate, trimethyl anilium tetraphenyl borate, methyl pyridinium tetraphenyl borate, benzyl pyridinium tetraphenyl borate, methyl tetraphenyl borate (2 -Cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyltetraphenylborate It can be given chill sulfonium.

Also, triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrabutyltetrakis (pentafluorophenyl) borate Ammonium, tetrakis (pentafluorophenyl) borate (tetraethylammonium), tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-
Butyl) ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis ( Methylanilinium pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), tetrakis (pentane Dimethyl fluorophenyl) borate (p-bromoanilinium).

Further, pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate ( N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (o-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate ( p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzylmethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetraphenylphosphonium, may be mentioned tetrakis (pentafluorophenyl) borate triphenylphosphonium tetrakis (3,5-ditrifluoromethylphenyl) borate dimethylanilinium, hexafluoroarsenate triethylammonium and the like.

Next, as the compound represented by the general formula [VIII], for example, ferrocenium tetraphenylborate,
Silver tetraphenylborate, trityl tetraphenylborate,
Tetraphenylborate (manganese tetraphenylporphyrin), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
(1,1′-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, Cyanofersenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis ( Pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (Pentafluorophenyl) borate (tetraphenylporphyrin zinc), mention may be made of silver tetrafluoroborate, tetra fluoro arsenic, silver hexafluoro antimonate and silver.

The component (B) used in the present invention is represented by the general formula [VII] or the general formula [VII]
Compounds other than the compound represented by I], for example, tri (pentafluorophenyl) boron, tri (3,5-di (trifluoromethyl) phenyl) boron, triphenylboron and the like can also be used. Further, in the method suitable for producing an α-olefin-based copolymer of the present invention, the component (C) optionally used in addition to the components (A) and (B) may be an organic aluminum as described above. Compound. Here, as the organoaluminum compound used as the component (C), specifically, the following general formulas [IX] and [X]
Or those represented by [XI].

That is, as the component (C), first, the general formula [IX]

Embedded image An organoaluminum compound represented by R ²³ Al _r Q _3-r ... [IX] is used. In the above formula, R ²³ has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
And a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, and an arylalkyl group. Q is a hydrogen atom,
It represents a halogen atom or an alkoxy group having 1 to 20 carbon atoms. Further, r is a number satisfying 1 ≦ r ≦ 3.

Specific examples of the organoaluminum compound represented by the general formula [IX] include, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum Examples thereof include dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

Next, the component (C) is represented by the general formula [X]

Embedded image A chain aluminoxane represented by the following formula is used. In the above formula, R ²³ have the same meanings as R ²³ in the above general formula [IX]. In addition, s indicates the degree of polymerization, and is usually 3 to 5
0, preferably 7 to 40.

Further, as the component (C), a compound represented by the general formula [X
I]

Embedded image A cyclic aluminoxane having a repeating unit represented by the following formula is used. In the above formula, R ²³ have the same meanings as R ²³ in the above general formula [IX]. S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.

Among the compounds represented by the above general formulas [IX], [X] or [XI], preferred are alkyl groups having 3 or more carbon atoms, especially alkyl groups having at least one branched alkyl group. Aluminum compound or aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained.

As a method for producing the above aluminoxane, there may be mentioned a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but 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 water is added later, and a crystal contained in a metal salt or the like. Water, a method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane and further reacting with water, a method of further reacting an active hydrogen group-containing compound with aluminoxane and modifying aluminoxane There is a way to get.

The catalyst used in the present invention is, as described above,
Component (A) and component (B) are the main components, or component (A), component (B) and component (C) are the main components. In this case, the use conditions of the component (A) and the component (B) are not particularly limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.01 to 1: 100, particularly 1: 0.5.
１ ： 1: 10, preferably 1: 1 to 1: 5. The temperature can be in the range of -100 ° C to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of the component (C) used in the present invention is generally from 0 to 200 per mol of the component (A).
0 mol, preferably 5 to 1000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the amount is too large, a large amount of the organic aluminum compound remains in the copolymer, which is not preferable. The use form of the catalyst is not limited. For example, 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 brought into contact in a polymerization system. May be used. Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance. The contact may be performed in advance or may be performed in a polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system. Further, the catalyst component can be used by being supported on an inorganic or organic carrier, if necessary.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is from -100C to + 250C, especially -50C.
To + 200 ° C. The proportion of the catalyst to the reaction raw material, the raw material monomer / component (A) (molar ratio), or the raw material monomer / component (B) (molar ratio) is 1 to 10 ^9, in particular 100 to 10 ⁷ and Preferably, Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 50 kg / cm ² G. Further, in order to adjust the molecular weight of the obtained norbornene-based copolymer, the amount of each catalyst component used and the polymerization temperature can be selected according to the purpose.
Further, the polymerization can be carried out in the presence of hydrogen. Thus, a norbornene-based copolymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in decalin at 135 ° C. can be produced.

When a polymerization solvent is used, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane Etc. can be used. One of these solvents may be used alone.
More than one species may be combined. Further, a monomer such as an α-olefin may be used as the solvent. The α-olefin polymer of the present invention may contain, if necessary, other elastomers and various additives, for example, stabilizers such as oxidizing materials, UV inhibitors, light stabilizers, heat stabilizers, and charged materials. , Anti-blocking agent, lubricant, slip agent, anti-fog agent, foaming agent, flame retardant, inorganic filler, organic filler, dye, content, etc.

The sheet or film of the present invention comprises the α-olefin polymer thus obtained. Here, in order to form a target sheet or film from the α-olefin-based polymer thus obtained, a general sheet or film forming method such as a T-die method or an inflation method can be adopted. A solvent casting method or the like can also be used. The sheet or film thus obtained can be further stretched to form a stretched sheet or film. The thickness of the sheet or film is not particularly limited, but is usually 1 μm to 10 mm, preferably 2 μm to 5 mm. The sheet or film of the present invention thus obtained has extremely high transparency,
It has excellent water resistance and flexibility.

[0062]

Next, the present invention will be described in detail with reference to examples. Example 1 (1) Synthesis of component (B) of catalyst (Jolly, WLThe Synthesis and Characterization of
Inorganic Compounds; Prentice-Hall: Englewood Cliff
s, NJ, 1970, P487) Ferrocene (Cp ₂ Fe) (3.7 g, 20.0 mmol)
And 40 ml of concentrated sulfuric acid (ml) were reacted at room temperature for 1 hour to obtain a dark blue solution. Add this dark blue solution to 1
Liter of water and stirred, and the resulting deep blue aqueous solution was treated with lithium tetra (pentafluorophenyl) borate (Li [B (C ₆ F ₅ ) ₄ ] (13.7 g, 20.0 mmol:
J. Organometal. Chem., Vol. 2 (1964), synthesized by the method described in P245). The falling pale blue precipitate was collected by filtration, washed five times with 500 ml of water, and dried under reduced pressure to obtain the desired product (ferrocenium tetra (pentafluorophenyl) borate) ([Cp ₂ Fe] [B _{(C 6 F 5) 4]} ) 14.7g was obtained.

(2) Polymerization In a 20-liter autoclave, 8 liters of dry toluene, 12 mmol of triisobutylaluminum as the component (C) of the catalyst, and tetra (butyl) obtained in the above (1) as the component (B) of the catalyst were used. 0.6 mmol of ferrocenium (pentafluorophenyl) borate, biscyclopentadienyl zirconium dimethyl 0.
6 mmol, and 4 mol of norbornene
at 50 ° C. and 5 kg / cm ² G ethylene pressure.
After polymerization for an hour, the polymerization was stopped with methanol. This was collected by filtration and dried to obtain 2.4 kg of a polymer. The polymerization conditions are shown in Table 1 below.

The polymerization activity was 44 kg / g · Zr. Further, it was determined from the ratio of the sum of the peak based on ethylene and the peak based on methylene at the 5th and 6th positions of the norbornene and the peak based on the methylene group at the 7th position of the norbornene which appeared near 32.5 ppm in ¹³ C-NMR. The norbornene content was 6 mol%. Furthermore, the intrinsic viscosity [η] measured in decalin at 135 ° C. is
2.10 dl / g, and the crystallinity determined by X-ray diffraction was 16%. This copolymer has a low degree of crystallinity and high transparency, indicating that it has a random structure. The glass transition temperature (Tg) was 4 m in width using Vibron II-EA type manufactured by Toyo Bolding Co., Ltd.
m, a measurement piece having a length of 40 mm was measured at a heating rate of 3 ° C./min. The molecular weight distribution (Mw / Mn) was measured using ALC / GPC150C manufactured by Waters Co., using 1,2,4-trichlorobenzene solvent at 135 ° C. in terms of polyethylene.

(3) Sheet Forming The copolymer obtained in (2) above was extruded using an extruder having a diameter of 20 mm under the conditions of a screw rotation speed of 30 rpm, a lip temperature of 205 ° C., and a lip opening of 0.5 mm. A sheet having a thickness of 0.2 mm was formed by T-die molding. The results of measuring physical properties such as the optical properties, elastic modulus, and elastic recovery of the obtained sheet are shown in Table 2 below.

Incidentally, the measurement of the total light transmittance in the evaluation of the optical characteristics is performed by a digital haze computer (DIGI).
TAL HAZE COMPUTER) (manufactured by Suga Test Machine Co., Ltd.). In addition, the measurement of the elastic modulus was performed using JI using an autograph.
It was determined according to S-K7113. Further, the elastic recovery was measured using an autograph at a tensile speed of 62 mm / min.
A test piece with a width of 6 mm and a clamp of 50 mm (L ₀ )
After stretching by 50% and pulling, maintaining the state for 5 minutes, suddenly shrinking without rebounding, measuring the sheet length (L ₁ ) between the clamps after 1 minute,
Determined by

Examples 2 to 7 Under the conditions shown in Table 1, various copolymers having different norbornene contents were synthesized using the same polymerization method as in Example 1.
A sheet having a thickness of 0.2 mm was prepared by a T-die method. However, the polymerization time of Example 7 was 110 minutes, different from the others. The results of measuring the physical properties of the obtained sheet are shown in the second section below.
It is shown in the table. Note that these copolymers have a low crystallization rate and high transparency, indicating that they have a random structure.

Comparative Example 1 Under the conditions shown in Table 1, the intrinsic viscosity [η] was 1.82 dl /
g, a copolymer of ethylene and norbornene having a norbornene content of 18.5 mol%. When a sheet having a thickness of 0.2 mm made from this copolymer was measured for elastic recovery, the sheet was broken before elongation by 150%, and no elastic recovery was obtained. The results of measuring the physical properties of the obtained sheet are shown in Table 2 below.

Comparative Example 2 A sheet having a thickness of 0.2 mm made of a commercially available high-density polyethylene (Idemitsu 640UF, manufactured by Idemitsu Petrochemical Co., Ltd.) had an elastic recovery of -50%. The results of measuring the physical properties of the obtained sheet are shown in Table 2 below.

Comparative Example 3 Copolymer of ethylene and α-olefin (Mooretec 01
68N, manufactured by Idemitsu Petrochemical Co., Ltd.)
The elastic recovery of the 2 mm sheet was -15%. The results of measuring the physical properties of the obtained sheet are shown in Table 2 below.

[0071]

[Table 1] Table 1

* 1: ZM: bis (cyclopentadienyl) dimethyl zirconium: ZC: bis (cyclopentadienyl) dichlorozirconium: ZC4: zirconium tetrachloride * 2: F: ferrocenium tetra (pentafluorophenyl) borate: AN ... Dimethylanilium tetra (pentafluorophenyl) borate * 3: TIBA ... Triisobutylaluminum * 4: Unit is kg / cm ² G

[0073]

[Table 2] Table 2

[0074]

The sheet or film made of the α-olefin copolymer of the present invention has a particularly excellent elastic recovery rate, maintains an appropriate elastic modulus, has a good balance of physical properties, and Because it has excellent transparency and water resistance,
It can be used very effectively in various fields such as the packaging field, the construction field, the medical field, and the agricultural field.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 5/18 C08F 210/00 C08F 232/00

Claims (5)

(57) [Claims] 1. A compound of the formula [I] (In the general formula [I], R ¹ represents a hydrogen atom.)
An α-olefin component having a repeating unit represented by the formula : a monocyclic olefin, a substituted monocyclic olefin and
And the general formula [II] (In the formula [II], R ^{2 to} R ¹³ each represent a hydrogen atom,
A hydrocarbon group of 1 to 20 or a halogen atom, oxygen
Represents a substituent containing an atom or a nitrogen atom, and n is 0 or
Indicates 1. Note that R ¹⁰ or R ¹¹ and R ¹² or
May form a ring with R ¹³ . Also, R ² ~
R ¹³ is, be the same as or different from each other
No. A) a cyclic olefin having a repeating unit represented by
A copolymer obtained by copolymerizing a cyclic olefin component selected from the group consisting of
g) a sheet or film comprising an α-olefin copolymer having a temperature of 30 ° C. or lower. 2. An α-olefin-based copolymer comprising α-ole
The repeating unit derived from the fin component is 82 to 99.9 m
% And repetition derived from the cyclic olefin component
Unit is in the range of 18 to 0.1 mol%, and 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.01
2. The sheet or fill according to claim 1, wherein the weight of the sheet or fill is from 20 to 20 dl / g.
M 3. A cyclic olefin represented by the general formula [II]:
3. The sheet according to claim 2, wherein n is 0.
Or film. 4. The method according to claim 1, wherein the elastic recovery is at least 10%.
The sheet or film according to claim 1, wherein: 5. The α-olefin component is ethylene,
The cyclic olefin component is norbornene;
90-98 mol% of repeating units derived from len and
When the repeating unit derived from rubornene is 10 to 2 mol%
The sheet or film according to claim 1.