JPH0782430A - Ethylenic copolymer composition - Google Patents

Abstract

PURPOSE:To provide an ethylenic copolymer composition comprising an ethylene-alpha-olefin copolymer, a specific ethylene-diene copolymer, etc., maintaining mechanical characteristics, excellent in transparency in a wide density range, and suitable for packaging materials, etc. CONSTITUTION:This ethylenic copolymer composition comprises (A) an ethylene-alpha-olefin copolymer having a density of 0.900-0.945g/cm<3>, etc., preferably in an amount of 1-99.9wt.% and (B) an ethylene-diene copolymer and/or an ethylene-alpha-olefin-diene terpolymer having a melt index (MI) measured under conditions comprising a temperature of 190 deg.C and a load of 2.16kg and an intrinsic viscosity [eta] measured in decalin at a temperature of 135 deg.C, the melt index and the intrinsic viscosity satisfying a relation of the inequality.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-based copolymer composition, and more specifically, it improves the transparency of an ethylene-α-olefin copolymer without lowering the density and improves the transparency in a wide density range. The present invention relates to an ethylene-based copolymer composition having excellent properties.

[0002]

2. Description of the Related Art Conventionally, ethylene-based (co) polymers have been widely used in many fields as general-purpose resins.
It has the following problems, and its improvement has been desired. For example, linear low density polyethylene (hereinafter, L-
LDPE) is superior in mechanical properties such as tensile strength and elastic modulus and heat resistance to low density polyethylene (hereinafter referred to as LDPE) prepared by a high pressure method, but its transparency is insufficient. . Also in the LDPE, the transparency is not sufficient. This transparency is improved by adjusting the kind and content of the comonomer to reduce the crystallinity, but in that case, there arises a problem that mechanical properties such as elastic modulus and strength are deteriorated. Further, in the L-LDPE obtained by using a homogeneous catalyst, the above problems can be solved to some extent, but the control of density and transparency cannot be said to be sufficient. On the other hand, Japanese Patent Publication No. 1-501555 discloses a non-crosslinkable copolymer obtained by polymerizing ethylene, 1,5-hexadiene and another comonomer. However, this publication only describes a linear or long-chain branched copolymer, and does not disclose a specific application of the composition such as a combination with a specific resin. Further, although the composition distribution of this ethylene-based copolymer is shown, the copolymer has a relatively high content of diene units (2 to 10 mol%).

[0003]

The present invention is based on ethylene-
An ethylene-based copolymer that improves transparency and retains excellent mechanical properties (high strength and elastic modulus) without decreasing the density of the α-olefin copolymer and has excellent transparency in a wide density range. The purpose of the invention is to provide a combined composition.

[0004]

[Means for Solving the Problems] The present inventors have conducted extensive studies to develop an ethylene-based copolymer composition having the above-mentioned preferable properties. As a result, an ethylene-α-olefin copolymer and a composition containing an ethylene-diene copolymer or an ethylene-α-olefin-diene copolymer having a specific relationship between the melt index (MI) and the intrinsic viscosity are obtained. , And found that it could be fit for that purpose. The present invention has been completed based on such findings. That is, the present invention relates to (a) an ethylene-α-olefin copolymer, and (b) a melt index (MI) measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg and an ultimate limit measured in decalin at a temperature of 135 ° C. The viscosity [η] contains an ethylene-diene copolymer and / or an ethylene-α-olefin-diene copolymer satisfying the relationship of the formula logMI ≦ 1.1-4.4 × log [η] An ethylene-based copolymer composition is provided.

In the composition of the present invention, an ethylene-α-olefin copolymer is used as the component (a).
The α-olefin used as a comonomer in the copolymer is preferably one having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-olefin.
1-Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. may be used, and these may be used alone or in combination. The above may be used in combination. The ethylene-α-olefin copolymer used as the component (a) has a density of 0.900 to 0.9.
45 g / cm ³ , preferably 0.900 to 0.940 g / c
Those in the range of m ³ are preferred. The ethylene-α-olefin copolymer may be used alone or in combination of two or more. The ethylene-α-
The method for producing the olefin copolymer is not particularly limited, and ethylene and the α-olefin may be copolymerized in the presence of a catalyst usually used for producing an ethylene-α-olefin copolymer. The catalyst may be a supported catalyst or a homogeneous catalyst.

In the composition of the present invention, the component (b) is an ethylene-diene copolymer and / or ethylene-α.
-Olefin-diene copolymers are used. Α-used in the ethylene-α-olefin-diene copolymer
As the olefin, those having 3 to 20 carbon atoms are preferable, for example, propylene, 1-butene, 1-pentene, 4
-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
—Hexadecene, 1-octadecene, 1-eicosene, etc. may be used, and these may be used alone or in combination of two or more. The diene compound used in the ethylene-diene copolymer or the ethylene-α-olefin-diene copolymer is a diene compound having two carbon-carbon polymerizable double bonds in the molecule, and the diene compound Is a compound formed from at least two same or different residues selected from α-olefin residues, styrene residues and cyclic olefin residues, and a polyfunctional compound selected from cyclic diene compounds. A polymerizable monomer is preferably used. Examples of such polyfunctional monomers include linear or branched acyclic diene compounds, monocyclic alicyclic diene compounds, polycyclic alicyclic diene compounds, cycloalkenyl-substituted alkenes, and aromatic rings. Examples of the diene compound include a diene compound having an α-olefin residue and a styrene residue in one molecule.

Examples of the linear or branched acyclic diene compound include 1,4-pentadiene; 1,4-hexadiene; 1,5-hexadiene; 1,6-octadiene;
1,7-octadiene; 1,9-decadiene; 1,11
-Dodecadiene; 2-methyl-1,4-pentadiene;
2-methyl-1,5-hexadiene; 3-ethyl-1,
7-octadiene and the like, and examples of the monocyclic alicyclic diene compound include 1,3-cyclopentadiene;
1,4-cyclohexadiene; 1,5-cyclooctadiene; 1,5-cyclododecadiene; 1,2-divinylcyclohexane; 1,3-divinylcyclohexane and the like. Examples of polycyclic alicyclic diene compounds include dicyclopentadiene, norbornadiene,
Tetrahydroindene, methyltetrahydroindene,
Bicyclo- (2,2,1) -hepta-2,5-diene,
5-methyl-2,5-norbornadiene, and norbornene of alkenyl, alkylidene, cycloalkenyl and cycloalkylidene, for example, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2. -Norbornene, 5-vinyl norbornene, 5-butenyl norbornene, 5-
(4-Cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, and formula

[0008]

[Chemical 1]

Examples include compounds represented by: Furthermore, examples of cycloalkenyl-substituted alkenes include allylcyclohexene, vinylcyclooctene, allylcyclodecene, vinylcyclododecene, and the like.
Examples of the diene compound having an aromatic ring include p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, di- (p-vinylphenyl) methane, 1,3.
Examples include -bis (p-vinylphenyl) propane and 1,5-bis (p-biphenyl) pentane. On the other hand, as the diene compound having a styrene residue as an α-olefin residue in one molecule, for example, p- (2-propenyl) styrene, m- (2-propenyl) styrene, p-
(3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p- (4-pentenyl) styrene, m- (4-pentenyl) styrene,
o- (4-pentenyl) styrene, p- (7-octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m
-(2-methyl-3-butenyl) styrene, o- (2-
Methyl-3-butenyl) styrene, p- (3-methyl-)
3-butenyl) styrene, p- (2-ethyl-4-pentenyl) styrene, p- (3-butenyl) -α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o- (3- Butenyl) -α-methylstyrene, 4-
Vinyl-4 '-(3-butenyl) biphenyl, 4-vinyl-3'-(3-butenyl) biphenyl, 4-vinyl-
4 '-(4-pentenyl) biphenyl, 4-vinyl-
2 '-(4-Pentenyl) biphenyl, 4-vinyl-
4 ′-(2-methyl-3-butenyl) biphenyl and the like can be mentioned. These diene compounds may be used alone or in combination of two or more.

In the composition of the present invention, the ethylene-diene copolymer or ethylene-α used as the component (b).
-The olefin-diene copolymer has a temperature of 190 ° C and a load.
Melt index (M
I) and the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. are expressed by the formula logMI ≦ 1.1-4.4 × log [η], preferably logMI ≦ 1.0-4.4 × log [η]. ] It is necessary to satisfy the relationship. If a copolymer that does not satisfy the above relationship is used, the object of the present invention cannot be achieved.

In the composition of the present invention, the ethylene-diene copolymer or ethylene-α-olefin-diene copolymer as the component (b) may be used alone or in combination of two or more. Good. The copolymer of the component (b) is used, for example, (A) a transition metal compound, (B) a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex, and if necessary. (C) In the presence of a polymerization catalyst containing an organoaluminum compound as a main component, ethylene and the diene compound or ethylene and the α
-It can be produced by copolymerizing an olefin and the diene compound. As the transition metal compound of the component (A), a compound containing a transition metal belonging to Groups 4 to 10 of the periodic table can be used. Specific examples of the transition metal include titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum, and the like. Among these, titanium, zirconium, hafnium, nickel, and palladium are particularly preferable.

[0012] As such a transition metal compound, various compounds can be mentioned, but a compound containing a transition metal selected from Group 4 of the periodic table, that is, a compound containing titanium, zirconium or hafnium is preferably used. You can
In particular, general formulas (I), (II), (III) 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 ··· ( cyclopentadienyl compounds and derivatives thereof represented by III) or general formula _{^{(IV) M 1 R 1 a}} R 2 b R 3 c R, Compounds represented by ⁴ _d (IV) and derivatives thereof are preferred.

In the above general formulas (I) to (IV), M ¹
Represents a transition metal such as titanium, zirconium or hafnium, and Cp represents cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted A cyclic unsaturated hydrocarbon group such as a fluorenyl group or a chain unsaturated hydrocarbon group is shown. R
¹ , R ² , R ³ and R ⁴ each independently represent a σ-bonding ligand, a chelating ligand, a ligand such as a Lewis base, and as the σ-bonding ligand, Specifically, hydrogen atom, oxygen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Examples of the 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, and the like, and a chelating ligand include acetyl. Examples thereof include an acetonate group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b, c, and d each independently represent an integer of 0 to 4, and e represents an integer of 0 to 6. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), two Cp
May be the same or different from each other.

Substituted cyclohexyl in the above formulas (I) to (III)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, the above (I)
R in formula (IV) ¹~ R^FourFor example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, ethylene;
Butadiene; 1-Pentene; Isoprene; Pentadie
Chain-unsaturated such as 1-hexene and their derivatives
Hydrocarbons, Benzene; Toluene; Xylene; Cyclohep
Tatriene; Cyclooctadiene; Cyclooctatriene
Such as cyclooctatetraene and derivatives thereof
Examples include cyclic unsaturated hydrocarbons. Also, the above formula (III)
Examples of the covalent cross-linking of A in
Tylene cross-link, dimethylmethylene cross-link, ethylene cross-link,
1,1'-cyclohexylene bridge, dimethylsilylene rack
Bridge, dimethylgermylene bridge, dimethylstannylene bridge
And so on.

Examples of the compound represented by the general formula (I) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl). Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadiene (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconi , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, Among these, compounds in which zirconium is replaced with titanium or hafnium are mentioned.

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis ( Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethane Cyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) dichlorozirconium and the like, as well as compounds in which zirconium is replaced with titanium or hafnium.

Examples of the compound represented by the general formula (III) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl).
Dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, etc. Alternatively, a compound can be given by substituting with hafnium.

Further, as the compound represented by the general formula (IV), for example, tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), and the like, and compounds in which zirconium is replaced with titanium or hafnium.

Further, as the component (A), in the general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). A group 4 transition metal compound having a multicoordinating compound as a ligand, which is bonded to each other via an element selected from group 14 of the periodic table, can be preferably used. Examples of such compounds include those represented by the general formula (V)

[0020]

[Chemical 2]

The compounds represented by
be able to. Y in the general formula (V)¹Is carbon, Kei
Element, germanium or tin atom, R^Five _t-C_FiveH_4-tOver
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R^Five
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists.
R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of 6-20, an alkylaryl group, or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R⁶Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁶ include methyl group, ethyl group, phenyl group, tolyl group, xylyl group, and benzyl group.

Specific examples of the compound represented by the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl). Examples thereof include cyclopentadienyl) titanium dichloride and dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride. Furthermore, general formula (VI)

[0024]

[Chemical 3]

It also includes compounds represented by: The general formula
In the compound of (VI), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is Si
R⁷ ₂, CR⁷ ₂, SiR⁷ ₂SiR⁷ ₂, CR⁷ ₂CR⁷ ₂, CR
⁷ ₂CR⁷ ₂CR⁷ ₂, CR⁷= CR⁷, CR⁷ ₂SiR⁷ ₂Or
GeR⁷ ₂Indicates Y ²Is -N (R⁸)-, -O-, -S-
Or -P (R⁸) -Indicates. R above⁷Is a hydrogen atom or 2
Alkyl, aryl, silyl having up to 0 non-hydrogen atoms
And alkyl halides, aryl halides and
R is a group selected from these combinations,⁸Has 1 to 1 carbon atoms
An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms
Yes, or one or more R⁷And up to 30
May form a fused ring system of non-hydrogen atoms. w is 1 or
2 is shown.

Specific examples of the compound represented by the above general formula (VI) include (tertiary butylamide) (tetramethyl-
η ⁵ -Cyclopentadienyl) -1,2-ethanediylzirconium dichloride; (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl titanium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl zirconium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride; (ethylamido) (tetramethyl- [eta] ⁵ -cyclopentadienyl)-
Methylene titanium dichloride; (tertiary butylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl; (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (phenylphosphide) dimethyl (tetramethyl- [eta] ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like. These transition metal compounds may be used alone or in combination of two or more.

In the polymerization catalyst, a compound capable of reacting with the transition metal compound or its derivative to form an ionic complex is used as the component (B). This (B)
As the component, (B-1) an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex,
Examples thereof include (B-2) aluminoxane and (B-3) Lewis acid.

As the component (B-1), any ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex can be used. General formula (VII), (VIII) ([L ¹ -R ⁹ ] ^{k +} ) _p ([Z] ^- ) _q ... (VII) ([L ² ] ^{k +} ) _p ([Z] ^- ) _q ···・ (VIII) (However, L ² is M ⁵ , R ¹⁰ R ¹¹ M ⁶ , R ¹² ₃ C or R
¹³ M ⁶ . ) [(VII), (VIII) In the formula, L ¹ is a Lewis base, [Z] ⁻
Is a non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 4 A 1 A 2 ···} A n] ^- (wherein, M ⁴ is periodic table 5-15 group element, preferably periodic table 13
Group 15 elements are shown. A ^{1 to} A ⁿ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to carbon atoms.
40 dialkylamino group, C1-20 alkoxy group, C6-20 aryl group, C6-20 aryloxy group, C7-40 alkylaryl group, C7-40 Arylalkyl group, carbon number 1
20 shows a halogen-substituted hydrocarbon group, a C1-C20 acyloxy group, an organic metalloid group, or a C2-C20 hetero atom-containing hydrocarbon group. 2 of A ^{1 to} A ⁿ
One or more may form a ring. n is [(central metal M
The valence of ⁴ ) +1]. ), [Z ^{2] -} is
The logarithm of the reciprocal of the acid dissociation constant (pKa) is -10 or less, and represents a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base generally defined as a super strong acid. Also, a Lewis base may be coordinated. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹⁰ and R ¹¹ respectively represent a cyclopentadienyl group and a substituted group. A cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is the ion valence of [L ¹ -R ⁹ ] and [L ² ] and is 1
˜3, p is an integer of 1 or more, and q = (k × p). M ⁵ contains an element of groups 1 to 3, 11 to 13 and ¹⁷ of the periodic table, and M ⁶ represents an element of groups 7 to 12 of the periodic table. ] What is represented by these can be used conveniently.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, and nitriles such as acetonitrile and benzonitrile. Specific examples of R ⁹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ¹⁰ and R ¹¹ include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group,
Examples thereof include a pentamethylcyclopentadienyl group. Specific examples of R ¹² include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ¹³ include tetraphenylporphine,
Examples thereof include phthalocyanine, allyl and methallyl. Further, specific examples of M ⁵ include Li, Na,
K, Ag, Cu, Br, I, I _{3 and the} like can be mentioned, and specific examples of M ⁶ include Mn, Fe, Co, Ni,
Zn etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ⁴ A ¹ A
² ... A ⁿ ], specific examples of M ⁴ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. As specific examples of A ¹ and A ^{2 to} A ⁿ , dimethylamino group, diethylamino group and the like as dialkylamino group, methoxy group, ethoxy group, n-butoxy group as alkoxy group or aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. As a hydrocarbon group containing iodine or a hetero atom, a p-fluorophenyl group, 3,
5-difluorophenyl group, pentachlorophenyl group,
Pentamethylantimony group, trimethylsilyl group, trimethyl as organic metalloid group such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combination conjugate base [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ⁻ , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{—, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The component (B-1), which is an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, may be used alone or in combination of two or more. You may use. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (IX)

[0034]

[Chemical 4]

(Wherein R ¹⁴ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and may independently be the same or different. s represents the degree of polymerization, and is usually 3 to 50, preferably 7 to
A chain aluminoxane represented by the formula (X) and a general formula (X)

[0036]

[Chemical 5]

(In the formula, R ¹⁴ and s are the same as the above), and the cyclic aluminoxane represented by the above can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

Further, the Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. A boron compound or an aluminum compound is preferably used as the organic compound, and a magnesium compound or an aluminum compound is preferably used as the inorganic compound.
Examples of the aluminum compound include bis (2,6-
Di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl and the like, magnesium compounds such as magnesium chloride and diethoxy magnesium, and aluminum compounds such as aluminum oxide. , Aluminum chloride, and the like, as the boron compound, for example, triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron. ，
Trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, Tris [3,3
5-bis (trifluoromethyl) phenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron and n-butyldifluoroboron. These Lewis acids may be used alone or in combination of two or more.

The ratio of the catalyst component (A) to the catalyst component (B) used in the polymerization catalyst is preferably 10 in terms of molar ratio when the compound (B-1) is used as the catalyst component (B). : 1 to 1: 100, more preferably 2: 1 to 1: 1.
The range of 10, more preferably 1: 1 to 1: 5 is desirable, and when the compound (B-2) is used, the molar ratio is preferably 1:20 to 1: 10000, more preferably 1: 100. The range of ˜1: 2000 is desirable. When the compound (B-3) is used, the molar ratio is preferably 10: 1 to 1: 2000, more preferably 5: 1 to 1: 1.
The range of 1: 1000, more preferably 2: 1 to 1: 500 is desirable. The polymerization catalyst may contain the above-mentioned component (A) and component (B) as main components, and may also contain the components (A), (B) and (C) organoaluminum compound. It may be contained as the main component. Here, the organoaluminum compound as the component (C) is represented by the general formula (XI) R ¹⁵ _r AlQ _3-r (XI) (wherein, R ¹⁵ has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms). Hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, and arylalkyl groups, Q is a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 20 carbon atoms, and r is 1 to 3
Is an integer. ) Is used.

Specific examples of the compound represented by the general formula (XI) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The (A) catalyst component and (C) catalyst component are preferably used in a molar ratio of 1: 1 to 1: 200.
The range of 0, more preferably 1: 5 to 1: 1000, and further preferably 1:10 to 1: 500 is desirable. By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

As the polymerization catalyst, at least one of catalyst components can be used by supporting it on a suitable inorganic carrier or organic carrier. As the inorganic carrier, for example, SiO ₂ , A
l ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ ,
B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, sepiolite, glass fiber, and magnesium compounds such as MgCl ₂ and Mg (OC ₂ H ₅ ) _2. Is mentioned. On the other hand, examples of the organic carrier include polymers such as polystyrene, styrene / divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. Among these carriers, especially MgCl
₂ , Mg (OC ₂ H ₅ ) ₂ , SiO ₂ and Al ₂ O ₃ are suitable. The average particle size of the carrier is 1 to 300 μm,
Preferably 10 to 200 μm, more preferably 20 to 1
The range of 00 μm is desirable. When ethylene, α-olefin and diene compound are used as monomers in the production of the copolymer of component (b), the molar ratio of diene compound: α-olefin is in the range of 1:10 ⁶ to 10 ² : 1. Is desirable. Regarding the polymerization conditions, the polymerization temperature is preferably as high as possible within the range where the catalytic activity is not impaired, and usually -1
It is selected in the range of 00 to 300 ° C, preferably -50 to 200 ° C, and more preferably 10 to 180 ° C. The polymerization pressure is preferably in the range of atmospheric pressure to 30 kg / cm ² G. Further, the ratios of the raw material monomer and the catalyst used are the same as those in the above (A).
It is desirable that the molar ratio with the catalyst component is 10 ⁷ : 1 to 10: 1, preferably 10 ⁶ : 1 to 10 ² : 1.

The polymerization method is not particularly limited, and any method such as slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method and suspension polymerization method may be used. The phase polymerization method is particularly preferred. 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 , 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 α-olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without a solvent. The molecular weight of the copolymer can be controlled by the ratio of the monomer to the catalyst used and the polymerization temperature. The ethylene copolymer composition of the present invention is an ethylene-diene copolymer and / or an ethylene-α-olefin-diene copolymer obtained by these production methods, that is, an ethylene-diene system containing at least a diene. Among the copolymers, an ethylene-diene copolymer (b) having a melt fluidity (melt index) (MI) having a specific relationship with the intrinsic viscosity [η] is used. Here, as the ethylene-diene copolymer (b), a constitutional unit derived from ethylene or ethylene and an α-olefin is 99.999 to 70 mol%, preferably 99.999 to 80 mol%, and more preferably 99.995-95 mol%, the structural unit derived from a diene is 0.001-30 mol%, preferably 0.001-
It is 20 mol%, more preferably 0.005 to 5 mol%. The MI is not particularly limited, but is usually 0.00
1 to 100 g / 10 minutes, preferably 0.005 to 50 g /
10 minutes. Furthermore, as [η], 0.1 to 30 dl /
g, preferably 0.2 to 20 dl / g. That is, logMI ≦ 1.1-4.4 × log [η], preferably logMI ≦ 1.0-4.4 × log [η], more preferably −1.5-15 × log [η] ≦ logMI ≦ 1 .0-4.4
Xlog [[eta]] most preferably -1.0-15 xlog [[eta]] ≤logMI≤1.0-4.4
× log [η] where the melt index (MI) is 190
It was measured under conditions of a temperature of 2.16 kg and a load of 2.16 kg, and the intrinsic viscosity [η] was measured in decalin at a temperature of 135 ° C. The transparency (haze) as the ethylene-diene copolymer (b) is not particularly limited, and even if the transparency (haze) is relatively poor, ethylene-
By blending with the α-olefin copolymer (a), the reason is not clear, but a remarkable improvement in transparency is observed.

The ethylene-based copolymer composition of the present invention can be prepared by homogeneously mixing at least one of the above-mentioned component (a) copolymer and at least one of the (b) component copolymer. it can. There are various methods for mixing, and for example, a method such as mixing in a molten state with a mixer or an extruder or mixing in a solution state can be used. In the ethylene-based copolymer composition of the present invention, the content of the component (a) is 1 to 99.9% by weight, preferably 5 to 99.5% by weight, more preferably 10 to 99% by weight, The content of the component (b) is 99 to 0.1% by weight, preferably 95 to 0.5% by weight, more preferably 90 to 1% by weight.
It is desirable to be in the range of. In the composition of the present invention, if necessary, other polymer may be added in an amount of 0.1 to 60 with respect to 100 parts by weight of the total amount of the components (a) and (b).
It may be contained in an amount of about part by weight, preferably 0.5 to 30 parts by weight. The ethylene-based copolymer composition of the present invention thus obtained retains a high degree of crystallinity. Therefore good mechanical properties (high strength, elastic modulus)
It is possible to provide a film, a sheet, a blow-molded product, and other molded products which have a significantly improved transparency.

[0044]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example A 1 liter pressure-resistant stainless steel autoclave was charged with toluene, 1-octene, norbornadiene (NBD), triisobutylaluminium (TIBA), methylaluminoxane (MAO) and dicyclopentadienylzirconium dichloride (Cp ₂ ZrCl ₂ ). The amount shown in Table 1 was added, and polymerization was carried out under the conditions shown in Table 1 to produce a copolymer. Melt index (MI), intrinsic viscosity [η], haze, logMI, 1.1 of the obtained copolymer
−4.4 × log [η] and density were obtained. The results are shown in Table 2. The MI is 190 ° C and the load is 2.16k.
It was measured under the condition of g, and [η] was determined by measuring viscosity at multiple concentrations in decalin at 135 ° C. The haze was press-molded at 190 ° C., cooled at a rate such that the temperature reached 150 ° C. in about 3 minutes to prepare a 0.1 mm-thick sheet, and this sheet was measured according to ASTM D1003-61. .

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

Table 3 shows the properties of commercially available polyethylene used in Examples and Comparative Examples.

[0049]

[Table 4]

Examples 1 to 7 and Comparative Example 1 The copolymers shown in Table 4 were used in the proportions shown in Table 4, and the contents were 3 at 190 ° C. in a Labo Plastomill manufactured by Toyo Seiki Seisakusho.
Using an 0 cc mixer, the mixture was kneaded at 20 rpm for 15 minutes to prepare an ethylene copolymer composition. The resulting composition is press molded at 190 ° C. for 150 minutes in about 3 minutes.
A sheet with a thickness of 0.1 mm is prepared by cooling at a rate such that the temperature becomes ℃, and this sheet is ASTM D1003-6.
The haze was measured according to 1. Further, the copolymer (a)
And the copolymer (b) were mixed to obtain a haze estimated by the following equation. Haze (calculated value) = [x × haze of copolymer (b)] +
[(1-x) x haze of copolymer (a)] Here, x is the copolymer (b) / [copolymer (a) + copolymer (b)] weight ratio. Further, the haze reduction rate calculated by the following formula was also obtained. Haze reduction rate (%) = [(calculated value−measured value) / (calculated value)] × 100 The results are shown in Table 4.

[0051]

[Table 5]

As can be seen from Table 4, the ethylene-based copolymer composition of the present invention has remarkably improved transparency.
Further, the effect of improvement is remarkable as compared with the composition of Comparative Example. Incidentally, the haze is a value when the press film is gradually cooled, and industrially, since the normal molding film is rapidly cooled,
Further, the effect of improving transparency can be expected.

[0053]

The ethylene-based copolymer composition of the present invention is
Good mechanical properties (high strength, elastic modulus) without reducing the density of the ethylene-α-olefin copolymer
The transparency is remarkably improved while maintaining the above, and it has excellent transparency in a wide density range and is suitable for use in various packaging materials such as films.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Shigeta 1280, Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (3)

[Claims] 1. An (a) ethylene-α-olefin copolymer, and (b) a melt index (MI) measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg and the limit measured in decalin at a temperature of 135 ° C. The viscosity [η] contains an ethylene-diene copolymer and / or an ethylene-α-olefin-diene copolymer satisfying the relationship of the formula logMI ≦ 1.1-4.4 × log [η] Ethylene copolymer composition. 2. The ethylene copolymer composition according to claim 1, wherein the ethylene-α-olefin copolymer as the component (a) has a density of 0.900 to 0.945 g / cm ³ . 3. The content of component (a) is 1 to 99.9% by weight.
The ethylene-based copolymer composition according to claim 1, wherein the content of the component (b) is 99 to 0.1% by weight.