JP2002327016A - Olefinic copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic copolymer having excellent resilience, shock- absorbability, transparency and moderate elastic modulus which is useful as a material of a film and sheet or the like. SOLUTION: The copolymer having a recurring unit derived from ethylene and a recurring unit derived from a cyclic olefin respectively has a content of the unit derived from ethylene of 80-99.9 mol% (1), an intrinsic viscosity [η]of 0.01-20 dl/g (2), a glass transition temperature (Tg) less than 30 deg.C (3) and a tensile modulus less than 2,000 kg/cm<2> (4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an appropriate elastic modulus and is excellent in elastic recovery, transparency and shock absorption, and is used for a sheet material and a molded article in a packaging field, a medical field, an agricultural field and the like. The present invention relates to an olefin copolymer suitably used as a molding material or the like.

[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.
Although it is mol%, there is a problem that the elastic modulus is high and the elastic recovery is extremely low. In addition, Japanese Unexamined Patent Publication No.
Japanese Patent No. 211315 discloses a random copolymer of an ethylene component and a specific cyclic olefin component having an ethylene content of 90 to 98 mol%.
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,
There is a limit to the use as a soft resin. Further, JP-A-2-276816 discloses an injection molded product comprising a copolymer of a specific cyclic olefin and ethylene. However, the copolymer disclosed in this publication has a drawback that the glass transition temperature (Tg) is as high as 50 to 230 ° C. and is inferior in impact resistance in a use temperature region near room temperature.

[0004] For this reason, there has been a demand for the development of a polyolefin-based resin having an excellent balance of various physical properties such as elastic recovery and elastic modulus. The present invention has been made in view of the above circumstances, and has excellent elastic recovery, transparency and shock absorption and an appropriate elastic modulus, and is used in various fields as a material for films, sheets and various molded articles. It is an object of the present invention to provide an olefin-based copolymer which can be effectively used as such.

[0005]

Means and Action for Solving the Problems The present inventors have
In order to solve the above-mentioned conventional problems and to provide a polyolefin resin excellent in balance of physical properties, such as having excellent elastic recovery property, and also having an appropriate elastic modulus, good transparency, and shock absorption, we have been conducting intensive research. Stacked. As a result, they found that a specific olefin copolymer containing an ethylene component and a small amount of a cyclic olefin component satisfied the required properties,
The present invention has been completed.

Accordingly, the present invention provides a copolymer having a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, wherein (1) the content of the repeating unit derived from ethylene is from 80 to 99. 9 mol%,
(2) intrinsic viscosity [η] of 0.01 to 20 dl / g,
(3) An olefin copolymer characterized by having a glass transition temperature (Tg) of less than 30 ° C. and (4) a tensile modulus of less than 2000 Kg / cm ² .

Hereinafter, the present invention will be described in more detail.
The olefin copolymer of the present invention has a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin.

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

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

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom
To 20 hydrocarbon groups or substituents containing a halogen atom, an oxygen atom or a nitrogen atom. 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 isopropyl group,
Alkyl groups having 1 to 20 carbon atoms such as -butyl group, isobutyl group, t-butyl group, hexyl group, etc .; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl. , A methylidene group, an ethylidene group, a propylidene group, etc.
Carbon number 2 such as alkylidene group, vinyl group, allyl group of 0
And -20 alkenyl groups. However,
R ^b , R ^c , R ^f and R ^g exclude an alkylidene group. Note that R
^{When any of d} , R ^e , and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

Specific examples of the substituent containing a halogen atom include halogen substituents having 1 to 20 carbon atoms such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specifically as a substituent containing a nitrogen atom,
Examples thereof 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 giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned. Among these, norbornene or a derivative thereof is particularly preferred.

The olefin-based copolymer of the present invention is basically obtained by copolymerizing ethylene and a cyclic olefin as described above. However, as long as the object of the present invention is not impaired, these essential components are used. In addition to the above two components, another copolymerizable unsaturated monomer component may be used as necessary. As such unsaturated monomers that may be optionally copolymerized, specifically, α-olefins other than ethylene,
Among the above-mentioned cyclic olefin components, those not previously used, cyclic dienes such as dicyclopentadiene and norbornadiene, butadiene, isoprene, 1,5
Chain diene such as hexadiene, cyclopentene,
Monocyclic olefins such as cycloheptene are exemplified.

In the olefin copolymer of the present invention, the content [x] of the ethylene unit and the content [y] of the cyclic olefin unit are [y] with respect to [x] of 80 to 99.9 mol%.
Is 20 to 0.1 mol%, preferably [x] is 82 to 9
[Y] is 18 to 0.5 mol% to 9.5 mol%, and particularly preferably [y] is 1 to 85 to 98 mol% for [x].
5 to 2 mol%. When the content [x] of the ethylene unit is less than 80 mol%, the glass transition temperature (Tg) and the tensile modulus of the copolymer become high, and the elastic recovery of the obtained film or sheet and the molded article Impact resistance,
Insufficient elasticity. On the other hand, when the content of the cyclic olefin unit [y] is less than 0.1 mol%, the crystallinity of the copolymer increases, and the effect of introducing the cyclic olefin component such as elastic recovery becomes insufficient.

The olefin copolymer of the present invention includes:
It is preferable that the copolymer is a substantially linear copolymer in which an ethylene unit and a cyclic olefin unit are linearly arranged, and 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.

Further, the olefin-based copolymer of the present invention comprises:
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.
It is necessary to be from 01 to 20 dl / g. If the intrinsic viscosity [η] is less than 0.01 dl / g, the strength is significantly reduced, and if it exceeds 20 dl / g, the moldability is significantly deteriorated. More preferred intrinsic viscosity [η] is 0.05 to 10 dl.
/ G.

The molecular weight of the olefin copolymer of the present invention is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) [in terms of polyethylene] is 1,000 to 2,2.
, 000,000, especially 5,000 to 1,000,000
0, number average molecular weight Mn is 500 to 1,000,000,
It is particularly preferably from 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 substance increases, which may cause stickiness when molded into a film, sheet, molded article or the like.

The olefin copolymer of the present invention needs to have a glass transition temperature (Tg) of less than 30 ° C. When such a copolymer is used, films, sheets, molded articles and the like which can be suitably used at low temperatures can be obtained. A more preferred glass transition temperature (Tg) is -30.
-20 ° C, especially -30 ° C to 15 ° C. In this case, the olefin copolymer of the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer, and the intended use, the temperature used, etc. The glass transition temperature (Tg) can be arbitrarily changed according to the conditions.

Further, the olefin copolymer of the present invention comprises:
The crystallinity measured by the X-ray diffraction method is preferably 0 to 40%. When the crystallinity exceeds 40%, elastic recovery and transparency may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The olefin copolymer of the present invention needs to have a tensile modulus of less than 2000 kg / cm ² . When the tensile modulus is 2000 kg / cm ² or more,
For example, when used for a packaging film, a large amount of energy is required at the time of packaging, and beautiful packaging suitable for the shape of the article to be packaged becomes difficult. In addition, when used for molded articles, impact resistance may be insufficient. A more preferred tensile modulus is 50 to 1,500 Kg / cm ² .

The olefin copolymer of the present invention preferably has an elastic recovery of 20% or more. If the elastic recovery is less than 20%, for example, when the article is wrapped, slack may occur or the holding force may decrease.
A more preferable elastic recovery rate is 30% or more, particularly 40% or more. The elastic recovery is a value measured by the method described in Example 1 described later.

[0021] The olefin copolymer of the present invention comprises a DSC
It is preferable that the broad melting peak by (measurement of temperature rise) is lower than 90 ° C. A copolymer having a sharp melting peak at 90 ° C. or higher by DSC (temperature rise measurement) has a wide composition distribution of a copolymer of cyclic olefin and ethylene, and has an elastic recovery property when molded into a film or the like. May be insufficient. In addition, it is more preferable that the broad melting peak by DSC (temperature rise measurement) is in the range of 10 to 85 ° C. In DSC (measurement of temperature rise), the melting point (melting peak) of the olefin-based copolymer of the present invention is not seen sharply, and especially in the case of those having a low crystallinity, almost no level is obtained at the level of ordinary polyethylene measurement conditions. No peak appears. The olefin copolymer of the present invention has a D
It is preferable that the crystallization peak by SC (temperature measurement) has one or more relatively small sub-peaks on the high temperature side of the main peak. Due to the above-mentioned characteristics of the thermal properties, the physical properties of the molded article can be obtained, and a molded article such as a high-quality film can be stably molded, for example, the molding temperature range is widened.

The olefin copolymer of the present invention includes:
It may be a copolymer consisting of only those having the physical properties in the above-mentioned range, or may be a copolymer partially containing a copolymer having physical properties out of the above-mentioned range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the olefin copolymer of the present invention is not limited, but a catalyst containing the following compounds (A) and (B) as main components or the following compounds (A), (B) and (C) is mainly used. Efficient production can be achieved by copolymerizing ethylene and a cyclic olefin using a catalyst as a component. (A) Transition metal compound containing titanium, zirconium or hafnium (B) Compound which reacts with transition metal compound (A) to form an ionic complex (C) Organoaluminum compound

As such a transition metal compound (A), various compounds may be mentioned. In particular, the following general formulas (I) and (I)
A cyclopentadienyl compound represented by (II) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. CpM ¹ R ¹ _a R ² _b R ³ _c (I) Cp ₂ M ¹ R ¹ _a R ² _b (II) (Cp-A _e -Cp) M ¹ R ¹ _a R ² _b.・ ・ (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV)

[In the formulas (I) to (IV), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group. A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a phenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), two Cp
May be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
V) Specific examples of R ^{1 to} R ^{4 in} the formula 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, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2 Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon 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 (III) include, for example, a methylene bridge, a dimethylmethylene bridge, an ethylene bridge, 1,1′-
Examples include cyclohexylene cross-link, dimethylsilylene cross-link, dimethylgermylene cross-link, and dimethylstannylene cross-link.

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

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

Compound of Formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo (Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
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

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkyl group, an alkoxy group, and a halogen atom, such as a compound in which zirconium is replaced with hafnium or titanium. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxytrichloro zirconium, dibutoxy dichloro zirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate)

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([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⁾

[Wherein L ¹ is a Lewis base,
M ³ and M ⁴ are VB, VIB, and VIIB of the periodic table, respectively.
Groups, VIII, IB, IIB, IIIA, IVA and VA
Element selected from the group, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, VII
Group I, IA Group, IB, Group IIA, 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, 6 carbon atoms
An aryloxy group having 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, acyloxy group, an organometalloid 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,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M ⁴
Is an integer of 1 to 7, n is an integer of 2 to 8, and k is [L
¹⁻ R ⁷ ], an integer of 1 to 7 in ionic valence of [L ² ], p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
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, S
b, etc., preferably B or P, as completely as examples of M ⁵ L
i, Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; 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; an 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-bis (trifluoromethyl) phenyl group; F, Cl, Br,
I; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. (V), (V
Among the compounds of the formula (I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V): triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltributyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate
Tetrabutylammonium borate, 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 (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

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, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Tetraphenylphosphonium pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triethylammonium hexafluoroarsenate

Compounds of Formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those of the formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron and triphenylboron can also be used. is there.

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; Represents an atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom. R is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, Examples include triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0041]

Embedded image (R ¹² is the same as in formula (VII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0042]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the number of repeating units is preferably from 3 to 50, and preferably from 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained. Further, a modified aluminoxane obtained by modifying the aluminoxane represented by the formulas (VII) to (IX) with a compound having active hydrogen such as water is also preferably used.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means 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 brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, 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 water.

The catalyst used in the production of the olefin-based copolymer of the present invention includes the above-mentioned components (A) and (B) or (A),
(B) and (C) are the 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:
It is preferably from 0.01 to 1: 100, particularly preferably from 1: 0.5 to 1:10, especially preferably from 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The component (C) is used in an amount of usually 0 to 2,000 mol, preferably 5 to 2,000 mol per mol of the component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable.

There is no limitation on the mode of use of the catalyst component. For example, the component (A) and the component (B) may be brought into contact in advance, or the contact product may be separated and washed before use. It may be used in contact. 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 made in advance, or may be brought into contact in the 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. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The usage 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 10 ⁹ , especially 1
It is preferable to be a 00-10 ^7.

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

Regarding the polymerization conditions, the polymerization temperature is -100 to 2
The temperature is preferably set to 50 ° C., particularly −50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 10 hours.
0 kg / cm ² G, preferably normal pressure to 50 kg / cm ² G
It is. As a method for adjusting the molecular weight of the copolymer, it is possible to select the amount of each catalyst component used and the polymerization temperature, and furthermore, to carry out the polymerization reaction in the presence of hydrogen.

The olefin copolymer of the present invention can be formed by a known method. 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, blow molding, rotational molding and the like can be performed using a screwless extruder or the like. Also, T-die molding method,
A film or sheet can be prepared by an inflation molding method or the like. In the molding process, if necessary, well-known additives such as a heat stabilizer, a light stabilizer,
Antistatic agents, slip agents, antiblocking agents, deodorants, lubricants, synthetic oils, natural oils, inorganic and organic fillers, dyes, pigments and the like may be added.

The olefin copolymer of the present invention has transparency, elastic recovery, impact absorption, adhesiveness, piercing strength, tear strength, weather resistance, low-temperature heat sealability, heat seal strength, impact strength, and shape. Because it is excellent in memory, dielectric properties, and narrow in molecular weight distribution and composition distribution and excellent in uniformity,
For example, sealant film, pallet stretch film, commercial wrap film, agricultural film, meat wrapping film, shrink film, coating material, vibration damping material, pipe, medical infusion pack, toy, or automobile parts, home appliance parts, wire and cable coating It can be used for various applications such as molded articles such as parts, civil engineering articles, and building materials.

[0052]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. The measuring method of each item in Examples and Comparative Examples is shown below. Norbornene content From the ratio of the sum of a peak based on ethylene and a peak based on methylene at the 5th and 6th positions of norbornene and a peak based on a methylene group at 7th position of the norbornene appearing at around 32.5 ppm, in ^13C -NMR, I asked. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Crystallinity Using a test piece prepared by hot pressing, X at room temperature
It was determined by a line diffraction method. Vibron 11 manufactured by Toyo Bolding Co., Ltd. as a glass transition temperature (Tg) measuring device
-Using EA type, width 4mm, length 40mm, thickness 0.1
mm measured piece heating rate 3 ° C. / min of, measured at a frequency 3.5 Hz, determined from the peak of loss modulus at this (E "). Mw, Mn , manufactured by Waters as Mw / Mn measurement device ALC / GPC-15
0C, column: TSK HM + GMH6X manufactured by Tosoh Corporation,
Solvent: 1,2,4-trichlorobenzene, liquid volume: 1.0
ml, temperature: 135 ° C., measured in terms of polyethylene. DSC temperature rise measurement: Perkin Elmer 7 series DS as a melting point (Tm) measurement device
Using C, at a heating rate of 10 ° C / min, -50 ° C to 150 ° C
It measured in the range of. DSC (measuring temperature drop): PerkinElmer 7 series DS as crystallization temperature measuring device
Using C, the sample was heated to 150 ° C. at 10 ° C./min, and
After holding for 0 seconds, the temperature was lowered to −50 ° C. at a rate of 10 ° C./min for measurement.

The tensile modulus, tensile strength at break, and tensile elongation at break were measured according to JIS-K7113 using an autograph. Using an elastic recovery autograph, a tensile speed of 62 mm / min and a width of 6 m
m, a measuring piece of 50 mm (L ₀ ) between the clamps was stretched by 150% and pulled, kept as it was for 5 minutes, then contracted suddenly without rebounding, and after 1 minute, the sheet length between the clamps (L ₁ ) was measured and determined by the following equation. Elastic recovery rate (%) = [1 − {(L ₁ −L ₀ ) / L ₀ }] ×
100 total light transmittance, Haze Digital Haze Computer (DIGITAL H
The measurement was performed using AZE COMPUTER (manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K7105.

Example 1 (1) Synthesis of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyl lithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was mixed with 45 mmol of boron trichloride in hexane. And tris (pentafluorophenyl) boron was obtained as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of lithium pentafluorophenyl, and lithium tetrakis (pentafluorophenyl) boron was isolated as a white solid. Next, 16 mmol of lithium tetrakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate as a white solid. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product.

(2) Copolymerization of ethylene and 2-norbornene At room temperature under nitrogen atmosphere, 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA) and 3 micromol of biscyclopentadienyl zirconium dichloride were placed in a 1-liter autoclave at room temperature. Then, 4 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in the above (1) is added in this order, and then 60 ml of a toluene solution containing 70% by weight of 2-norbornene (400 mol of 2-norbornene) is added. After the temperature was raised to 90 ° C., the ethylene partial pressure was 7
The reaction was carried out for 90 minutes while continuously introducing ethylene so as to obtain Kg / cm ² . After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, and the polymer was collected by filtration and dried.

(3) Sheet Forming The copolymer obtained in the above (2) was used at a temperature of 190 ° C.
Pressure 100Kg / cm ^TwoPerform hot press molding with thickness
A 0.1 mm sheet was made.

Table 1 shows the catalyst components, polymerization conditions and the like in Example 1, and Table 2 shows the physical properties of the obtained copolymer and sheet. In the copolymer of Example 1, a broad melting peak was observed at 75 ° C. Figure 1 shows DSC (heating measurement)
The chart is shown.

Example 2 (1) Preparation of ferrocenium tetrakis (pentafluorophenyl) boron 20 mmol of ferrocene (Cp ₂ Fe) and concentrated sulfuric acid 40
of the solution was reacted at room temperature for 1 hour to obtain a dark blue solution. This dark blue solution is poured into 1 liter of water and stirred, and the resulting deep blue aqueous solution is mixed with tetrakis (pentafluorophenyl)
It was added to 500 ml of an aqueous solution of 20 mmol of lithium 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 tetrakis (pentafluorophenyl) borate ([Cp ₂ Fe] [B (C ₆ F _{5) 4])} 17
Mmol was obtained.

(2) Copolymerization of ethylene and 2-norbornene In Example 1 (2), instead of dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate prepared in (1) above Polymerization was carried out in the same manner as in Example 1 (2), except that ferrocenium was used and other conditions were as shown in Table 1. (3) Forming of sheet Using the copolymer obtained in (2), the same procedure as in Example 1 (3) was performed.

Table 1 shows the catalyst components, polymerization conditions and the like in Example 2. Table 2 shows the physical properties of the obtained copolymer and sheet.

Examples 3 to 6 (1) (2) Preparation of catalyst and copolymerization of ethylene and 2-norbornene The same procedures as in Example 1 were carried out except that the catalyst components and polymerization conditions were changed as shown in Table 1. Thus, a copolymer was obtained. (3) Forming of sheet Using the copolymer obtained in (2), the same procedure as in Example 1 (3) was performed.

Table 1 shows the catalyst components and polymerization conditions in Examples 3 to 6, and Table 2 shows the physical properties of the obtained copolymer and sheet.
Shown in In the copolymer of Example 3, a broad melting peak was observed at 77.0 ° C. FIG. 2 shows a DSC (temperature rise measurement) chart. Further, the copolymer of Example 3 had two sub-peaks (74 ° C., 96.1 ° C.) on the high temperature side of the main crystallization temperature peak (54.8 ° C.). FIG. 3 shows a DSC chart. FIG. 4 shows a ¹³ C-NMR chart of the copolymer of Example 4.

Example 7 (1) Preparation of Catalyst In the same manner as in Example 1 (1), dimethylanilinium tetrakis (pentafluorophenyl) borate was synthesized. (2) Copolymerization of ethylene and 2-norbornene In a 1-liter autoclave, 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), and dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in (1) above were added. After charging 03 mmol, bis (cyclopentadienyl) dimethylzirconium 0.03 mmol, and 2-norbornene 200 mmol, the mixture was polymerized at 50 ° C. and an ethylene pressure of 5 kg / cm ² for 30 minutes, and then terminated with methanol. This was collected by filtration and dried to obtain 26.4 g of a copolymer. (3) Forming of sheet Using the copolymer obtained in (2), the same procedure as in Example 1 (3) was performed.

Table 1 shows the catalyst components, polymerization conditions and the like in Example 7, and Table 2 shows the physical properties of the obtained copolymer and sheet. In the copolymer of Example 7, a broad melting peak was observed at 82.8 ° C. FIG. 5 shows a DSC (temperature rise measurement) chart. The copolymer of Example 7 had a subpeak (7) on the high temperature side of the main crystallization temperature peak (62 ° C.).
8 ° C., 98 ° C.). Figure 6 shows DS
The C chart is shown. Further, ¹³ C of the copolymer of Example 7 was used.
FIG. 7 shows an NMR chart.

Comparative Example 1 (1) Copolymerization of ethylene and 2-norbornene Under a nitrogen atmosphere, 400 ml of toluene, 8 mmol of ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) were placed in a 1-liter autoclave, (O
C ₂ H ₅₎ Cl ₂ 0.8 mmol, 2-norbornene 20
After the temperature was raised to 40 ° C., the reaction was carried out for 180 minutes while continuously introducing ethylene so that the ethylene partial pressure became 3 kg / cm ² . After the reaction was completed, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, which was collected by filtration and dried. (2) Forming of sheet Using the copolymer obtained in (1), the same procedure as in Example 1 (3) was performed.

Table 1 shows the catalyst components and polymerization conditions in Comparative Example 1, and Table 2 shows the physical properties of the obtained copolymer and sheet. In the copolymer of Comparative Example 1, a sharp melting peak was observed at 100 ° C. FIG. 8 shows a DSC (heating measurement) chart. The copolymer of Comparative Example 1 had no sub-peak on the high temperature side of the main crystallization temperature peak (64.5 ° C.). FIG. 9 shows a DSC (temperature drop measurement) chart. Comparing FIGS. 3 and 6 with FIG. 8, the copolymer of the example has a sub-peak on the high temperature side of the main crystallization temperature peak, whereas the copolymer of the comparative example does not have such a sub-peak. Understand. It is considered that the large difference between the two elastic recovery rates is due to such a difference in thermal properties.

Comparative Example 2 (1) (2) Preparation of catalyst and copolymerization of ethylene and 2-norbornene Copolymer was prepared in the same manner as in Example 1 except that the catalyst components and polymerization conditions were changed as shown in Table 1. A polymer was obtained. (3) Forming of sheet Using the copolymer obtained in (2), the same procedure as in Example 1 (3) was performed. Table 1 shows the catalyst components, polymerization conditions and the like in Comparative Example 2, and Table 2 shows the physical properties of the obtained copolymer and sheet.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

As described above, the olefin-based copolymer of the present invention has excellent elastic recovery, transparency, impact absorption and an appropriate elastic modulus, and is excellent in physical balance. It can be effectively used as a material of a film or a sheet or a molding material of a molded article in various fields such as a packaging field, a medical field, and an agricultural field.

[Brief description of the drawings]

FIG. 1 is a DSC (temperature rise measurement) chart of the copolymer of Example 1.

FIG. 2 is a DSC (temperature rise measurement) chart of the copolymer of Example 3.

FIG. 3 is a DSC (measurement of temperature drop) chart of the copolymer of Example 3.

FIG. 4 is a ¹³ C-NMR chart of the copolymer of Example 4.

FIG. 5 is a DSC (temperature rise measurement) chart of the copolymer of Example 7.

FIG. 6 is a DSC (measurement of temperature drop) chart of the copolymer of Example 7.

FIG. 7 is a ¹³ C-NMR chart of the copolymer of Example 7.

8 is a DSC (temperature rise measurement) chart of the copolymer of Comparative Example 1. FIG.

FIG. 9 is a DSC (temperature decrease measurement) chart of the copolymer of Comparative Example 1.

 ──────────────────────────────────────────────────の Continued on the front page (72) Junichi Matsumoto, Inventor 1280, Kamiizumi, Sodegaura-shi, Chiba Prefecture (72) Takuji Okamoto, 1280, Kamiizumi, Sodegaura-shi, Chiba (72) Inventor Masami Watanabe, Kamiizumi, Sodegaura-shi, Chiba 1280 F term (reference) 4J100 AA02P AR09Q AR11Q AR22Q AS15Q AU21Q BA05Q BA31Q BA40Q BB01Q BB07Q BC04Q BC43Q DA04 DA09 DA25 DA49 JA44 JA67 5G305 AA02 AB40 BA12 CA01 CA51

Claims (10)

[Claims] 1. A copolymer having a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, wherein (1) the content of the repeating unit derived from ethylene is 80 to 99.9 mol%, (2) intrinsic viscosity [η] is 0.01 to 20 dl / g, and (3) glass transition temperature (T
g) is less than 30 ° C., and (4) the tensile modulus is 2000 kg /
An olefin-based copolymer characterized by being less than ² cm ² . 2. A copolymer comprising only a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, wherein (1) the content of the repeating unit derived from ethylene is 80 to 99.9 mol%, (2) Intrinsic viscosity [η]
Is 0.01 to 20 dl / g, and (3) glass transition temperature (T
g) is less than 30 ° C., and (4) the tensile modulus is 2000 kg /
less than cm ^2, (5) an olefin-based copolymer Mw / Mn is characterized from 1.3 to 1.91. 3. A copolymer having a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, wherein (1) the content of the repeating unit derived from ethylene is 82 to 99.5 mol%, (2) intrinsic viscosity [η] is 0.01 to 20 dl / g, and (3) glass transition temperature (T
g) is less than 30 ° C., and (4) the tensile modulus is 2000 kg /
less than cm ^2, (5) an olefin-based copolymer Mw / Mn is characterized from 1.3 to 1.91. 4. A copolymer having a repeating unit derived from ethylene and a repeating unit derived from norbornene, wherein (1) the content of the repeating unit derived from ethylene is 80 to 99.9 mol%, (2) intrinsic viscosity [η] is 0.01 to 20 dl / g, and (3) glass transition temperature (T
g) is less than 30 ° C., and (4) the tensile modulus is 2000 kg /
less than cm ^2, (5) an olefin-based copolymer Mw / Mn is characterized from 1.3 to 1.91. 5. A repeating unit derived from ethylene, and a compound represented by the following general formula [Y]: (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents 0. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. A) a copolymer having a repeating unit derived from a cyclic olefin represented by (1), wherein the content of the repeating unit derived from ethylene is 93 to 99.9 mol%,
The content of the repeating unit derived from the cyclic olefin is 7 to
0.1 mol%, (2) intrinsic viscosity [η] is 0.01 to 20
An olefin-based copolymer characterized by dl / g, (3) a glass transition temperature (Tg) of less than 30 ° C., and (4) a tensile modulus of less than 2000 kg / cm ² . 6. A toy using the olefin-based copolymer according to any one of claims 1 to 5. 7. A pipe using the olefin-based copolymer according to any one of claims 1 to 5. 8. An electric cable covered part using the olefin copolymer according to claim 1. Description: 9. A building material using the olefin copolymer according to any one of claims 1 to 5. 10. A civil engineering article using the olefin-based copolymer according to any one of claims 1 to 5.