JP3387995B2 - Ethylene copolymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an ethylene-based copolymer composition, and more specifically, it has improved thermal stability and moldability as compared with a conventionally known ethylene-based copolymer or an ethylene-based copolymer composition. The present invention relates to an ethylene-based copolymer composition capable of producing a film having excellent balance between transparency and rigidity.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when an inflation film is to be molded at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform a stable high speed molding, the melt tension (melt tension) of the ethylene-based copolymer should be considered for its molecular weight. You have to choose the bigger one. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding.

By the way, a method of improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in Japanese Patent Laid-Open No. 56-90810. Japanese Patent Laid-Open No. 60-106806 and the like. However, in general, an ethylene-based polymer obtained by using a titanium-based catalyst, particularly a low-density ethylene-based copolymer, has a wide composition distribution and has a problem that a molded product such as a film is sticky.

Among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts are relatively excellent in melt tension but poor in thermal stability. There are disadvantages. It is considered that this is because the chain end of the ethylene polymer produced using the chromium catalyst is likely to be an unsaturated bond.

Among the Ziegler type catalyst systems, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded product such as a film is less sticky. However, for example, in JP-A-60-35007, an ethylene-based polymer obtained by using a zirconocene compound containing a cyclopentadienyl derivative as a ligand as a catalyst has one terminal unsaturated bond per molecule. It is described that it contains, and like the ethylene polymer obtained by using the chromium catalyst, the thermal stability is expected to be poor.

Therefore, if an ethylene polymer having a high melt tension, good thermal stability, excellent mechanical strength and a narrow composition distribution appears, its industrial value is extremely high.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is an ethylene-based copolymer which can produce a film having excellent moldability and excellent balance of transparency and rigidity. The purpose is to provide a combined composition.

[0008]

SUMMARY OF THE INVENTION A first ethylene copolymer composition according to the present invention comprises [A1] (a) an organoaluminum oxy compound and (b) a transition metal compound represented by the following general formula [I].
At least one kind ^{_{chosen, ML 1 X ... [I]}} ( wherein M is a transition metal raw selected from Group IVB of the periodic table
A child, L ¹ is Ah in ligand coordinating to the transition metal atom M
Ri, ligand L ¹ at least two of these, sik
Lopentadienyl group, methylcyclopentadienyl group,
Ethyl Le cyclopentadienyl group or 3 to 10 carbon atoms,
Having at least one group of that selected from the group consisting of hydrocarbon radicals
A substituted cyclopentadienyl group, (substituted) cyclopentyl
The ligand L ¹ other than the naphthadienyl group has 1 to 12 carbon atoms.
Hydrocarbon group, alkoxy group, aryloxy group, trial
A silyl group, a halogen atom or a hydrogen atom, and X
Is the valence of the transition metal M. ) Shown by the following general formula [II]
At least one selected from the following transition metal compounds and ML ² _X ... [II] (wherein M is a transition metal precursor selected from Group IVB of the periodic table).
A child, L ² is Ah in ligand coordinating to the transition metal atom
And at least two of these ligands L ² are
2 to 3 substituents selected from the group
A substituted cyclopentadienyl group having a substituted cyclopentadienyl group
Ligand L ² other than pentadienyl group, 1 to 12 carbon atoms
Hydrocarbon groups, alkoxy groups, aryloxy groups , thoria
An alkyl group, a halogen atom or a hydrogen atom,
X is a valence of the transition metals atom M. ) Consisting of less
And a ligand having two cyclopentadienyl skeletons
In the presence of an olefin polymerization catalyst containing a transition metal compound of Group IV of the periodic table containing ethylene and α having 3 to 20 carbon atoms.
-Obtained by copolymerizing with an olefin, (i) the density is in the range of 0.850 to 0.980 g / cm ³ , and (ii) the melt flow rate (MFR) at 190 ° C and a load of 2.16 kg. It is in the range of 0.01 to 200 g / 10 minutes, and (iii) the melt tension (MT) at 190 ° C.
(G)) and the melt flow rate (MFR) satisfy the relationship ^represented by the following formula MT> 2.2 × MFR ^−0.84 , and (iv) the shear stress at 190 ° C. of the melt copolymer is 2.
The fluidity index (FI (1 / sec)) defined by the shear rate when reaching 4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) satisfy the relationship represented by FI <150 × MFR. 60 to 99% by weight of an ethylene / α-olefin copolymer, and [B] 1 to 40% by weight of at least one crystalline polyolefin selected from the following groups (B-I) to (B-III). (B-I) a melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg of 0.01 to 100 g / 10 min, a density of more than 0.900 g / cm ³ , and ethylene. A homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms (provided that ethylene.
(Excluding α-olefin copolymer [A1]) (B-II) Melt flow rate (MFR) at 230 ° C and 2.16 kg load is in the range of 0.1 to 100 g / 10 minutes, and density is 0.900 g. / Cm ³ or more, a propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and α-olefins having 4 to 20 carbon atoms (B-III) 230 ° C, 2.16 kg. Melt flow rate (MFR) under load is in the range of 0.1 to 100 g / 10 minutes, density is more than 0.900 g / cm ³ , homopolymer of α-olefin having 4 to 20 carbon atoms, or carbon number. Copolymers of 4 to 20 α-olefins.

[0009]

The second ethylene-based copolymer composition according to the present invention comprises: [A2] ethylene and carbon number in the presence of the above-mentioned olefin polymerization catalyst.
By copolymerizing with 3 to 20 α-olefins
The resulting, (i) the density is in the range of ^{0.850~0.980g / cm 3, (ii)} 190 ℃, melt flow rate at 2.16kg load (MFR) of 0.01 to 200 g / 10 min Within the range, (iii) melt tension at 190 ° C. (MT
(G)) and the melt flow rate (MFR) satisfy the relationship ^represented by the following formula MT> 2.2 × MFR ^−0.84 , and (iv) the shear stress at 190 ° C. of the melt copolymer is 2.
The fluidity index (FI (1 / sec)) defined by the shear rate when reaching 4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) satisfy the relationship represented by FI <150 × MFR. , (V) the molecular weight distribution (Mw / Mn) measured by GPC is in the range of 1.5 to 4, (vi) MT / (Mw / Mn) and FI / MFR are MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (However, the value of 0.03 × FI / MFR-3.0 is 0
60 to 99% by weight of an ethylene / α-olefin copolymer satisfying the relationship represented by the following formula: [B] at least one selected from the following groups (B-I) to (B-III) (B-I) melt flow rate (MFR) at 190 ° C. and 2.16 kg load is in the range of 0.01 to 100 g / 10 min. , An ethylene homopolymer having a density of more than 0.900 g / cm ³ , or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms (provided that the ethylene.
(Excluding α-olefin copolymer [A1]) (B-II) Melt flow rate (MFR) at 230 ° C and 2.16 kg load is in the range of 0.1 to 100 g / 10 minutes, and density is 0.900 g. / Cm ³ or more, a propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and α-olefins having 4 to 20 carbon atoms (B-III) 230 ° C, 2.16 kg. Melt flow rate (MFR) under load is in the range of 0.1 to 100 g / 10 minutes, density is more than 0.900 g / cm ³ , homopolymer of α-olefin having 4 to 20 carbon atoms, or carbon number. Copolymers of 4 to 20 α-olefins.

Such an ethylene-based copolymer composition is
It is possible to produce a film having excellent moldability and excellent balance of transparency and rigidity.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The ethylene copolymer composition according to the present invention will be described in detail below. A first ethylene-based copolymer composition according to the present invention comprises an ethylene / α-olefin copolymer [A1] and a crystalline polyolefin [B], and a second ethylene-based copolymer according to the present invention. The composition is an ethylene / α-olefin copolymer [A
2] and crystalline polyolefin [B].

[Ethylene / α-olefin copolymer] The ethylene / α-olefin copolymers [A1] and [A2] which form the ethylene copolymer composition according to the present invention.
Is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the C3-C20 α-olefin used for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-.
Examples include pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

In such ethylene / α-olefin copolymers [A1] and [A2], the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 50% by weight.
99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight and having 3 to 2 carbon atoms.
0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 50% by weight of the structural unit derived from the α-olefin of 0.
It is desirable to be present in an amount of 35% by weight, most preferably 4-30% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample in which about 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at the measurement temperature. 120
℃, measurement frequency 25.05MHz, spectrum width 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of.

The ethylene / α-olefin copolymer [A which forms the first ethylene-based copolymer composition according to the present invention.
[1] preferably has the characteristics as shown in the following (i) to (iv), and more preferably has the characteristics as shown in the following (i) to (ix). Further, the ethylene / α-olefin copolymer [A2] forming the second ethylene-based copolymer composition according to the present invention has the following (i) to (v
It is preferable to have the characteristics shown in i), and it is more preferable to have the characteristics shown in the following (i) to (ix).

(I) The density (d) is 0.850 to 0.98.
0 g / cm ³ , preferably 0.880 to 0.960 g / c
m ³ , more preferably 0.890 to 0.935 g / cm ³ ,
Most preferably, it is desirable to be in the range of 0.905 to 0.930 g / cm ³ .

The density (d) is 2.
The strand obtained at the time of measuring the melt flow rate (MFR) under a load of 16 kg was heat treated at 120 ° C. for 1 hour, and
After slowly cooling to room temperature over time, measurement is performed with a density gradient tube.

(Ii) The melt flow rate (MFR) is
0.01 to 200 g / 10 minutes, preferably 0.05 to 50
g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

The melt flow rate (MFR) is
Measured according to ASTM D1238-65T under conditions of 190 ° C. and 2.16 kg load. (Iii) Melt tension (MT (g)) and melt flow rate (MFR) are MT> 2.2 × MFR ^−0.84, preferably 8.0 × MFR ^−0.84 >MT> 2.3 × MFR ^{−0.84 Preferably} satisfies the relationship of 7.5 × MFR ^−0.84 >MT> 2.5 × MFR ^−0.84 .

Since such an ethylene / α-olefin copolymer has a high melt tension (MT), it has good moldability. In addition, melt tension (MT (g))
Is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, the produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample. Using an MT measuring device manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, and a winding speed of 10 to 20 m / min. The nozzle diameter was 2.09 mm and the nozzle length was 8 mm. When pelletizing, ethylene
To the α-olefin copolymer, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- ( 0.1% by weight of 4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added.

(Iv) Shear stress at 190 ° C. is 2.4
The fluidity index (FI (1 / sec)) and the melt flow rate (MFR) defined by the shear rate when reaching × 10 ⁶ dyne / cm ² are FI <150 × MFR, preferably FI <140 × MFR. It is more desirable that the relationship represented by FI <130 × MFR is satisfied.

The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using a sample similar to MT measurement, manufactured by Toyo Seiki Seisakusho,
It is measured with a capillary flow characteristic tester at a resin temperature of 190 ° C. and a shear stress range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

The MFR of the resin to be measured (g / 10 minutes)
Change the nozzle diameter as follows and measure. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR

(V) Molecular weight distribution measured by GPC (Mw
/ Mn, where Mw: weight average molecular weight, Mn: number average molecular weight) is preferably in the range of 1.5 to 4. The molecular weight distribution (Mw / Mn) is GPC manufactured by Millipore.
It measured using -150C as follows.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
T (Takeda Yakuhin) 0.025% by weight was used, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. . Standard polystyrene has a molecular weight of Mw <10
00 and Mw> 4 × 10 ⁶ were manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ were manufactured by Pressure Chemicals.

(Vi) MT / (Mw / Mn) and FI / MF
R and MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (provided that the value of 0.03 × FI / MFR-3.0 is 0 when it is less than 0). 0.03 × FI / MFR + 1.0> MT / (Mw / Mn)
> 0.03 × FI / MFR-2.8 (however, the value of 0.03 × FI / MFR-2.8 is 0 when it is less than 0), more preferably 0.03 × FI / MFR + 0.8. > MT / (Mw / Mn)
> 0.03 × FI / MFR-2.5 (where the value of 0.03 × FI / MFR-2.5 is 0 when it is less than 0) is preferably satisfied.

Since the MT value increases as the Mw / Mn value increases, the MT / (Mw / Mn) index was used to reduce the influence of the Mw / Mn value on the MT value. Similarly, since the FI value increases with an increase in the MFR value, the FI / MFR index was used to reduce the influence of the MFR value on the FI value.

(Vii) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.)) and the density (d) are represented by Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550 × d-391. It is desirable to meet the relationship.

The temperature (Tm (° C)) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
Raise the temperature to 0 ° C and hold at 200 ° C for 5 minutes, then at 20 ° C
It can be obtained from the endothermic curve when the temperature is decreased to room temperature at the speed of 10 / min, and then the temperature is increased at 10 ° C./min. For the measurement, a Perkin Elmer DSC-7 type device is used.

(Viii) When the n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at 23 ° C. are MFR ≦ 10 g / 10 min, W <80 × exp (-100 ( d-0.88)) + 0.1, preferably W <60 * exp (-100 (d-0.8)
8)) + 0.1, more preferably W <40 × exp (−100 (d−0.8)
8)) + 0.1 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

N of the ethylene / α-olefin copolymer
-The amount of soluble components in decane (the smaller the amount of soluble components, the narrower the composition distribution) is about 3 g of the copolymer n-decane 450.
In addition to ml, the solution was dissolved at 145 ° C., cooled to 23 ° C., the n-decane-insoluble part was removed by filtration, and the n-decane-soluble part was recovered from the filtrate.

Relationship between the temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) and the density (d), and the n-decane soluble component amount fraction (W)
It can be said that the ethylene / α-olefin copolymer having the above-described relationship between the density and the density (d) has a narrow composition distribution.

(Ix) The number of unsaturated bonds present in the molecule is preferably 0.5 or less per 1000 carbon atoms and less than 1 per molecule of the polymer. The unsaturated bond was quantified by ¹³ C-NMR using a signal other than the double bond, that is, a signal in the range of 10 to 50 ppm, and a signal belonging to the double bond, ie, 10.
The area intensity of the signal in the range of 5 to 150 ppm is obtained from the integral curve and is determined from the ratio.

Ethylene / α-having the above characteristics
The olefin copolymers [A1] and [A2] are prepared, for example, from (a) an organoaluminum oxy compound and (b) a transition metal compound represented by the following general formula [I].
At least one kind ^{_{chosen, ML 1 X ... [I]}} ( wherein M is a transition metal raw selected from Group IVB of the periodic table
A child, L ¹ is Ah in ligand coordinating to the transition metal atom M
Ri, ligand L ¹ at least two of these, sik
Lopentadienyl group, methylcyclopentadienyl group,
Ethyl Le cyclopentadienyl group or 3 to 10 carbon atoms,
Having at least one group of that selected from the group consisting of hydrocarbon radicals
A substituted cyclopentadienyl group, (substituted) cyclopentyl
The ligand L ¹ other than the naphthadienyl group has 1 to 12 carbon atoms.
Hydrocarbon group, alkoxy group, aryloxy group, trial
A silyl group, a halogen atom or a hydrogen atom, and X
Is the valence of the transition metal M. ) Shown by the following general formula [II]
At least one selected from the following transition metal compounds and ML ² _X ... [II] (wherein M is a transition metal precursor selected from Group IVB of the periodic table).
A child, L ² is Ah in ligand coordinating to the transition metal atom
And at least two of these ligands L ² are
2 to 3 substituents selected from the group
A substituted cyclopentadienyl group having a substituted cyclopentadienyl group
Ligand L ² other than pentadienyl group, 1 to 12 carbon atoms
Hydrocarbon groups, alkoxy groups, aryloxy groups , thoria
An alkyl group, a halogen atom or a hydrogen atom,
X is a valence of the transition metals atom M. ) Consisting of less
And a ligand having two cyclopentadienyl skeletons
In the presence of a catalyst for olefin polymerization containing a Group IV transition metal compound containing ethylene, ethylene and an α-olefin having 3 to 20 carbon atoms are added, and the density of the resulting copolymer is 0.8.
It can be produced by copolymerizing so as to have a concentration of 50 to 0.980 g / cm ³ , but it is (a) an organoaluminum oxy compound, at least two (b) transition metal compounds, and (c) as described below. In the presence of a carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and a carbon number of 3 to 2 are present.
When the α-olefin of 0 is copolymerized, the ethylene / α-olefin copolymer as described above can be produced with high polymerization activity.

Hereinafter, the ethylene / α-olefin copolymer [A, which forms the ethylene copolymer composition according to the present invention,
The catalyst components used in the polymerization of [1] and [A2] will be described.

First, the organoaluminum oxy compound (a)
Will be described.

The organoaluminum oxy compound (a) (hereinafter sometimes referred to as the "component (a)") used in the present invention may be a conventionally known benzene-soluble aluminoxane. It may be a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-276807.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of reacting by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of.

(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable. Further, as the organoaluminum compound, represented by the following general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (x, y, z are each a positive number, the z ≧ 2x) Isoprenylaluminum may also be used.

The above organoaluminum compound is
Used alone or in combination. As the solvent used in the production of aluminoxane, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil. And hydrocarbon solvents such as halides of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 times that of the organoaluminum oxy compound corresponding to 100 mg of Al.
After suspending in 0 ml of benzene and mixing under stirring at 60 ° C for 6 hours, the solid portion separated on the filter was subjected to filtration at 60 ° C using a jacketed G-5 glass filter while hot. Amount of Al atoms present in all the filtrates after washing 4 times with 50 ml of benzene at ℃ (x
It is determined by measuring (mmol) (x%).

Next, (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton will be described. The (b) transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component (b)”) used in the present invention is specifically described. Is a transition metal compound represented by the following formula [I] or [II].

ML ¹ _X ... [I] (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand coordinated to the transition metal atom M, and At least two of the ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ML ² _X ... [II] (wherein M is a transition metal atom selected from Group IVB of the Periodic Table, L ² is a ligand coordinated to the transition metal atom, and at least 2 of these are included). The individual ligand L ² is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and the ligand L ² other than the substituted cyclopentadienyl group is 1 to 12 carbon atoms
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) Hereinafter, the transition metal compound represented by the general formula [I] or [II] will be described more specifically.

In the above formula [I], M is IV of the periodic table.
A transition metal atom selected from Group B, specifically zirconium, titanium or hafnium, preferably zirconium.

L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are
At least one selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or a hydrocarbon group having 3 to 10 carbon atoms.
It is a substituted cyclopentadienyl group having certain substituents. These ligands may be the same or different. The ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents include a methyl group and an ethyl group. Alternatively, it is a hydrocarbon group having 3 to 10 carbon atoms.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Examples thereof include an alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neofil group.

Of these, alkyl groups are preferable, and n-propyl group and n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group coordinated to the transition metal is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms, A substituted cyclopentadienyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.

In the above general formula [I], the ligand L ¹ other than the (substituted) cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, It is an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically, a methyl group, an ethyl group and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, alkyl group such as decyl group; cyclopentyl group, cyclohexyl group, etc. A cycloalkyl group of phenyl group,
Examples thereof include aryl groups such as tolyl group; and aralkyl groups such as benzyl group and neophyll group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group. Can be illustrated.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Halogen atoms are fluorine, chlorine, bromine and iodine.

Examples of the transition metal compound represented by the general formula [I] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (ethylcyclopentadienyl) zirconium. Dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopenta) Dienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (N-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium diethoxide,
Bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl)
Zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butyl) Cyclopentadienyl)
Zirconium hydride chloride, and the like. In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is
Includes 1,2,3- and 1,2,4-substitutes. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [I], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1 -Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

In the above general formula [II], M is the periodic table
A transition metal atom selected from Group IVB, specifically,
Zirconium, titanium or hafnium, preferably zirconium.

L ² is a ligand coordinated to the transition metal atom M, and at least two ligands L ² among them have only 2 to 5 substituents selected from a methyl group and an ethyl group.
And substituted cyclopentadienyl groups, each of which may be the same or different. The substituted cyclopentadienyl group is a substituted cyclopentadienyl group having two or more substituents, preferably a substituted cyclopentadienyl group having two to three substituents, and a disubstituted cyclopentadienyl group. An enyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.
In addition, each substituent may be the same or different.

In the above formula [II], the ligand L ² other than the substituted cyclopentadienyl group coordinated to the transition metal atom M has the same carbon number of 1 as that of L ¹ in the above formula [I]. ~ 1
2 is a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

Examples of the transition metal compound represented by the general formula [II] include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride and bis (methylethylcyclopentadienyl). ) Zirconium dichloride Bis (dimethylethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis (dimethylcyclopentadienyl) zirconium methoxychloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride , Bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium diethoxide, bis (dimethylcyclopentadiene Nil) zirconium methyl chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium Examples thereof include phenyl chloride and bis (dimethylcyclopentadienyl) zirconium hydride chloride. In the above example, the disubstituted cyclopentadienyl ring is
Includes 1,2- and 1,3-substitutions, tri-substitutions include 1,2,3- and
Includes 1,2,4-substitutes. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [II], bis (1,3-dimethylcyclopentadienyl) zirconium dichloride and bis (1,3-diethylcyclopentadienyl) zirconium dichloride ,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride is particularly preferred.

In the present invention, when producing the ethylene / α-olefin copolymers [A1] and [A2], at least the transition metal compound represented by the above general formula [I] is used as the transition metal compound (b). It is preferable to use one kind in combination with at least one kind selected from the transition metal compounds represented by the general formula [II].
Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (1.3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propylmethylcyclohexyl) Pentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) A combination with zirconium dichloride is preferred.

At least one transition metal compound selected from the transition metal compounds (bI) represented by the general formula [I], and the transition metal compound (b-
The at least one transition metal compound selected from II) is 99/1 to 50/50, preferably 97/3 to 70/30, and more preferably 95 / in terms of molar ratio (bI / b-II).
5-75 / 25, most preferably 90 / 10-80 / 2
It is desirable to use it in such an amount that the range is 0.

Hereinafter, the term "component (b)" means at least one selected from the transition metal compounds (bI) represented by the above general formula [I] and the transition metal represented by the above general formula [II]. It may mean a transition metal compound catalyst component containing at least one selected from the compound (b-II).

The carrier (c) used in the present invention (hereinafter sometimes referred to as "component (c)") is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 300 μm. A 200 μm granular or particulate solid is used. Among them, the inorganic compound is preferably a porous oxide, and specifically, SiO ₂ , Al ₂ O ₃ , MgO,
ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ or the like or a mixture thereof, such as SiO ₂ -MgO, SiO
_2- Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -C
Examples thereof include r ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The above inorganic oxide contains a small amount of Na ₂ CO.
₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al
₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (N
It does not matter even if it contains a carbonate, a sulfate, a nitrate or an oxide component such as O ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a carrier (c) vary depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. , The pore volume is 0.3-
It is preferably 2.5 cm ³ / g. The carrier is, if necessary, 100 to 1000 ° C, preferably 150 to 70 ° C.
It is used after firing at 0 ° C.

In such carrier (c), it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.0% by weight. 5 to 4.0% by weight, particularly preferably 2.0 to 3.5
It is desirable that the content is wt%.

Here, the amount of water adsorbed on the carrier (c) (% by weight)
And the amount of surface hydroxyl groups (% by weight) is determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Amount of surface hydroxyl groups (% by weight) = {(X-Y) /
X} × 100 Furthermore, examples of the carrier (c) that can be used in the present invention include granular or particulate solids of an organic compound having a particle size in the range of 10 to 300 μm. Examples of these organic compounds include α-C 2 -C 14 such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
Examples thereof include (co) polymers containing olefin as a main component, and polymers or copolymers containing vinylcyclohexane and styrene as main components.

The catalyst used in the present invention includes the above-mentioned (a) organoaluminum oxy compound and at least two kinds of (b)
Formed from a transition metal compound and (c) a carrier,
You may use the (d) organoaluminum compound as needed.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) which is used as necessary include, for example, the organoaluminum compounds represented by the following general formula [III]. can do.

R ¹ _n AlX _3-n ... [III] (In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and X 1
Is a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [III], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n- Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of the organoaluminum compound (d) include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, (d) an organoaluminum compound
It is also possible to use a compound represented by the following general formula [IV]
it can. R¹ _nAlY_3-n  … [IV] (In the formula, R¹Is the same as above, and Y is -OR²Group,-
OSiR³ ₃Group, -OAlR ^Four ₂Group, -NR^Five ₂Group, -SiR⁶ ₃
Group or -N (R⁷) AlR⁸ ₂And n is 1-2.
R², R³, R^FourAnd R⁸Is a methyl group, an ethyl group,
Sopropyl group, isobutyl group, cyclohexyl group,
Such as a nyl group, R^FiveIs hydrogen atom, methyl group, ethyl
Group, isopropyl group, phenyl group, trimethylsilyl group
And so on, R⁶And R⁷Is a methyl group, ethyl group, etc.
Is. ) Specific examples of such an organoaluminum compound include
The following compounds are used. (1) R¹ _nAl (OR²)_3-nA compound represented by
Methyl aluminum methoxide, diethyl aluminum
Ethoxide, diisobutylaluminum methoxide
What (2) R¹ _nAl (OSiR³ ₃)_3-nA compound represented by
If Et₂Al (OSi Me₃), (Iso-Bu)₂Al (OSiMe₃),
(iso-Bu)₂Al (OSiEt₃) Such; (3) R¹ _nAl (OAlR^Four ₂)_3-nCompounds represented by
If Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)
₂Such; (4) R¹ _nAl (NR^Five ₂)_3-nA compound represented by, for example
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt,
Et₂AlN (SiMe₃)₂, (Iso-Bu)₂AlN (SiMe₃)₂ Na
Th; (5) R¹ _nAl (SiR⁶ ₃)_3-nA compound represented by, for example
(iso-Bu)₂AlSiMe₃ Such; (6) R¹ _nAl (N (R⁷) AlR⁸ ₂)_3-nCompound represented by
Thing, eg Et₂AlN (Me) AlEt₂, (Iso-Bu)₂AlN
(Et) Al (iso-Bu)₂Such .

[0081] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ¹ ₃ Al,
The compounds represented by R ¹ _n Al (OR ² ) _3-n and R ¹ _n Al (OA1R ⁴ ₂ ) _3-n are preferable, and the compound in which R is an isoalkyl group and n = 2 is particularly preferable.

In the present invention, when the ethylene / α-olefin copolymers [A1] and [A2] are produced, the above-mentioned component (a), component (b) and component (c),
A catalyst prepared by bringing the component (d) into contact with each other, if necessary, is preferably used. Component (a) in this case
The contacting order of the component (d) is arbitrarily selected, but preferably, the component (c) and the component (a) are mixed and contacted, then the component (b) is mixed and contacted, and if necessary, the component (d) is added. ) Are mixed and contacted. The component (b) is preferably prepared by mixing in advance two or more transition metal compounds forming the component (b) and then mixing and contacting with other components.

The contact of the above components (a) to (d) can be carried out in an inert hydrocarbon solvent, and specific examples of the inert hydrocarbon solvent used for preparing the catalyst include propane, butane, Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride , Halogenated hydrocarbons such as chlorobenzene and dichloromethane, or a mixture thereof.

When the component (a), the component (b) and the component (c) and, if necessary, the component (d) are mixed and contacted, the component (b) is usually added in an amount of 5 × 10 5 g / g of the component (c).
^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, and the concentration of component (b) is about 10 ^-4 to 2
× 10 ^-2 mol / liter (solvent), preferably 2 × 10
It is in the range of ^-4 to 10 ^-2 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum of the component (a) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. Atom ratio (Al-d / Al-a) of aluminum atom (Al-d) of component (d) and aluminum atom (Al-a) of component (a) that are used as necessary.
Is usually in the range of 0.02 to 3, preferably in the range of 0.05 to 1.5. The mixing temperature for mixing and contacting the component (a), the component (b), the component (c), and optionally the component (d) is usually -50 to 150 ° C, preferably -20 to 120.
And the contact time is 1 minute to 50 hours, preferably 10
Minutes to 25 hours.

The olefin polymerization catalyst (solid catalyst component) thus obtained has 5 × 10 ^{−6 to} 5 × 10 5 of transition metal atoms derived from the component (b) per 1 g of the component (c).
^-4 gram atom, preferably loaded in an amount of 10 ^-5 to 2 x 10 ^-4 gram atom, and also component (a) per gram of component (c).
And the aluminum atom derived from the component (d) is 10 ⁻³
~ 5x10 ^-2 gram atom, preferably 2x10 ^-3 to 2x
It is preferably loaded in an amount of 10 ^-2 gram atom.

In the present invention, the olefin polymerization catalyst used in the production of the ethylene / α-olefin copolymer is the above-mentioned component (a), component (b) and component (c),
It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of the component (d) if necessary. Prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned component (a), component (b) and component (c), and optionally in the coexistence of component (d). Can be done by. The solid catalyst component is preferably formed from the components (a) to (c).
In this case, in addition to the solid catalyst component, component (a) and / or component (d) may be further added.

The olefins used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1 -Octene, 1-decene, 1
Examples include -dodecene and 1-tetradecene. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

In the prepolymerization, the above component (b) is
It is usually 1 in terms of the transition metal atom derived from the component (b).
It is used in an amount of 0 ^{−6 to} 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the component (b) per 1 g of the component (c). , Usually 5 × 10
It is used in an amount of ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol. The atomic ratio (Al / transition metal) of aluminum of the component (a) to the transition metal in the component (b) is
It is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-a) of the component (a), which are used as necessary, is usually 0.02 to 3, preferably in the range of 0.05 to 1.5. Prepolymerization temperature is -2
The temperature is 0 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The prepolymerization catalyst is specifically prepared, for example, as follows. That is, the carrier (component (c)) is suspended in inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to this suspension, and the mixture is reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon. A transition metal compound (component (b)) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Then, the preliminarily polymerized catalyst is obtained by adding the solid catalyst component obtained above to an inert hydrocarbon containing an organoaluminum compound (component (d)), and introducing olefin into it.

The amount of the olefin (co) polymer produced by the prepolymerization is 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g, per 1 g of the carrier (c). desirable. Further, in the prepolymerization catalyst, the component (b) is about 5 as transition metal atoms per 1 g of the carrier (c).
× 10 ^{-6 to} 5 × 10 ^-4 gram atom, preferably 10 ^-5 to
The aluminum atom (Al) derived from the component (a) and the component (d), which is supported in the amount of 2 × 10 ⁻⁴ gram atom, is
The molar ratio (Al / M) to the transition metal atom (M) derived from the component (b) is 5 to 200, preferably 10 to 15.
It is desirable that the amount is carried in the range of 0.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

The ethylene / α-olefin copolymers [A1] and [A2] which form the ethylene-based copolymer composition of the present invention are treated with ethylene in the presence of the above-mentioned olefin polymerization catalyst. , Α-C3-20
Olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1
It is obtained by copolymerizing -decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the liquid phase in the form of a slurry. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples include petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When carrying out the slurry polymerization method or the gas phase polymerization method, the above-mentioned catalyst usually has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ^-8 to 10 ^-3 g atom / min.
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In the polymerization, in addition to the organoaluminum oxy compound (component (a)) and the organoaluminum compound (component (d)) supported on the carrier, the organoaluminum oxy compound and / or the organic aluminum oxy compound and / or the organic aluminum oxy compound not supported on the carrier are further added. An aluminum compound may be used. In this case, the atomic ratio of the aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and / or the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (b) (Al / M ) Is 5
The range is 0 to 300, preferably 10 to 200, and more preferably 15 to 150.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C., and when carrying out the gas phase polymerization method, The polymerization temperature is usually 0 to 120 ° C., preferably 20.
Is in the range of -100 ° C

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. [Crystalline Polyolefin [B]] The crystalline polyolefin [B] forming the ethylene-based copolymer composition according to the present invention is at least one crystal selected from the following (B-I) to (B-III). It is a polyolefin.

"Crystalline Polyolefin (B-I)" The crystalline polyolefin (B-I) is an ethylene homopolymer having a crystallinity of 65% or more as measured by X-ray diffractometry, or a crystallinity of 65. % Or more of ethylene and 3 to 20 carbon atoms
Is a copolymer of α-olefin with 190 ° C, 2.1
Melt flow rate (MFR) under a load of 6 kg is 0.01 to 100 g / 10 minutes, preferably 0.05 to 50
It is in the range of g / 10 minutes and has a density of 0.900 g / cm ^3.
Beyond, it is desirable that preferably in the range of 0.930~0.970g / cm ^3.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Can be mentioned. Of these, it is particularly preferable to use an α-olefin having 3 to 10 carbon atoms. Further, in such a copolymer, ethylene and α
-Molar ratio with olefin (ethylene / α-olefin)
Is generally 100/0 to 99/1, preferably 100/0 to 99, though it varies depending on the type of α-olefin.
It is 5 / 0.5.

The crystalline polyolefin (B-I) is
A component unit other than the α-olefin-derived component unit such as a diene compound-derived component unit may be contained within a range that does not impair the characteristics.

Examples of the constituent unit other than the constituent unit derived from the α-olefin include, for example, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl- Chain non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5- Methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl
Cyclic non-conjugated dienes such as 2-norbornene; Diene compounds such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene The component units derived from can be mentioned.

The diene components can be used alone or in combination. The content of the diene component is
It is usually 0 to 1 mol%, preferably 0 to 0.5 mol%. Such crystalline polyolefin (B-I) can be produced by a conventionally known method.

In the first ethylene copolymer composition, a crystalline polyolefin other than the ethylene / α-olefin copolymer [A1] is used as the crystalline polyolefin (B-I). In the ethylene-based copolymer composition, the crystalline polyolefin excluding the ethylene / α-olefin copolymer [A2] is used as the crystalline polyolefin (B-I).

[Crystalline Polyolefin (B-II)] The crystalline polyolefin (B-II) is a propylene homopolymer having a crystallinity of 50% or more as measured by X-ray diffraction, or propylene, ethylene and carbon. Number 4-20 α-
A copolymer with at least one olefin selected from olefins, which has a crystallinity of 30% or more, and a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of 0.1. 1-100g / 10 minutes,
It is preferably in the range of 0.5 to 50 g / 10 minutes and has a density of more than 0.900 g / cm ³ , preferably 0.900 to
It is preferably in the range of 0.920 g / cm ³ .

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. You can Of these, carbon number 4 to 1
It is particularly preferred to use 0 α-olefins.

Propylene, ethylene and carbon number 4 to
In the copolymer with at least one selected from 20 α-olefins, propylene, ethylene and C 4
The molar ratio of propylene to α-olefin (propylene / α-olefin (including ethylene)) varies depending on the type of α-olefin, but is generally 100/0 to 90/1.
It is 0, preferably 100/0 to 95/5.

The crystalline polyolefin (B-II) is
A component unit derived from the diene compound used for the crystalline polyolefin (B-I) as described above may be contained within a range that does not impair the characteristics. The content of the diene component is usually 0 to 1 mol%, preferably 0 to 0.5.
Mol%.

Such crystalline polyolefin (B-II)
Can be produced by a conventionally known method. "Crystalline Polyolefin (B-III)" The crystalline polyolefin (B-III) is a homopolymer of an α-olefin having 4 to 20 carbon atoms and having a crystallinity of 30% or more measured by an X-ray diffraction method, Or a copolymer of α-olefins having 4 to 20 carbon atoms with a degree of crystallinity of 30% or more, 23
Melt flow rate (MFR) at 0 ° C. under a load of 2.16 kg is 0.1 to 100 g / 10 minutes, preferably 0.1.
It is in the range of 5 to 50g / 10 minutes and has a density of 0.900g.
/ Cm ^3, preferably greater 0.900~0.920g /
The range of cm ³ is desirable.

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Of these, it is particularly preferable to use an α-olefin having 4 to 10 carbon atoms.

At least two or more α having 4 to 20 carbon atoms
-In the olefin copolymer, one α-olefin (a) selected from α-olefins having 4 to 20 carbon atoms
And the other α-olefin (b) selected from α-olefins having 4 to 20 carbon atoms ((a) / (b))
Is generally 100/0 to 90/10, preferably 100/0 to 95, though it varies depending on the type of α-olefin.
/ 5.

Crystalline polyolefin (B-III)
May contain a component unit or the like derived from the diene compound used in the crystalline polyolefin (B-I) as described above, as long as the characteristics thereof are not impaired. The content of the diene component is usually 0 to 1 mol%, preferably 0 to
It is 0.5 mol%.

Such crystalline polyolefin (B-II
I) can be produced by a conventionally known method. [Ethylene-based copolymer composition] The first ethylene-based copolymer composition according to the present invention comprises the ethylene / α-olefin copolymer [A1] and a crystalline polyolefin [B]. .Α-Olefin copolymer [A1]
And the crystalline polyolefin [B] in a weight ratio ([A
1]: [B]) is 99: 1 to 60:40, preferably 9
5: 5 to 70:30, more preferably 95: 5 to 80:
A range of 20 is desirable.

The second ethylene-based copolymer composition according to the present invention is the ethylene / α-olefin copolymer [A
2] and the crystalline polyolefin [B], and the weight ratio ([A2]: [B]) of the ethylene / α-olefin copolymer [A2] and the crystalline polyolefin [B] is 9
9: 1 to 60:40, preferably 95: 5 to 70: 3
It is preferably 0, more preferably 95: 5 to 80:20.

The ethylene-based copolymer composition of the present invention can be produced by a known method, for example, the following method. (1) The ethylene / α-olefin copolymer [A1] (or [A2]), the crystalline polyolefin [B], and optionally other components are mechanically added using an extruder, a kneader, or the like. How to blend.

(2) The ethylene / α-olefin copolymer [A1] (or [A2]), the crystalline polyolefin [B], and optionally other components are added to a suitable good solvent (eg, hexane, A hydrocarbon solvent such as heptane, decane, cyclohexane, benzene, toluene and xylene), and then removing the solvent.

(3) The ethylene / α-olefin copolymer [A1] (or [A2]), the crystalline polyolefin [B], and optionally other components are separately dissolved in a suitable good solvent. The method of preparing the above solution, mixing them, and then removing the solvent.

(4) A method in which the above methods (1) to (3) are combined. The ethylene-based copolymer composition of the present invention has a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, within a range that does not impair the object of the present invention. Additives such as pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, and antioxidants may be blended as necessary.

The ethylene copolymer composition of the present invention is processed into a film by ordinary air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooling inflation molding and the like. Obtainable. The film thus formed has an excellent balance of transparency and rigidity, and has the heat sealability, hot tack property, heat resistance and the like which are the features of ordinary LLDPE. Further, since the composition distribution of the ethylene / α-olefin copolymer is extremely narrow, the film surface is not sticky. Furthermore, since the melt tension is high, the bubble stability during inflation molding is excellent.

The film obtained by processing the ethylene-based copolymer composition of the present invention is a standard bag, sugar bag,
It is suitable for various packaging films such as oil packaging bags and water packaging bags and agricultural materials. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

[0122]

The ethylene-based copolymer composition of the present invention is
Since a specific ethylene / α-olefin copolymer is blended with a specific crystalline polyolefin, it is possible to produce a film that has excellent moldability and fluidity in the high shear range, as well as excellent balance of transparency and rigidity. You can

[0123]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In the present invention, the physical properties of the film were evaluated as follows. [Haze] Measured according to ASTM-D-1003-61.

[Tensile test] A dumbbell (JIS No. 1) was used to punch a test piece in the machine direction (MD) and the transverse direction (TD) with respect to the film forming direction, and the distance between chucks was 86 m.
m, crosshead speed 200 mm / min. The tensile modulus (YM) and the elongation at break (EL) were measured by.

[0126]

[Production Example 1] [Ethylene / α-olefin copolymer polymerization] [Preparation of catalyst component] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 liters of toluene and then cooled to 0 ° C. did. Then, a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) 28.
7 liters were dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and reacted at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. To this system was added 6.6 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and bis (1.3-dimethylcyclopentadienyl) zirconium. 2.0 l of a toluene solution of dichloride (Zr; 28.1 mmol / l) was added dropwise at 80 ° C over 30 minutes, and further reacted at 80 ° C for 2 hours. afterwards,
By removing the supernatant and washing twice with hexane,
A solid catalyst was obtained containing 3.6 mg of zirconium per gram.

[Preparation of prepolymerized catalyst] In 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1-
Hexene (255 g) was added and ethylene was prepolymerized at 35 ° C. for 12 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The [η] of this ethylene polymer was 1.74 dl / g.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. The prepolymerized catalyst prepared above was converted into zirconium atoms at 0.18 mmol / h and triisobutylaluminum at 10 mmol / h.
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.030, hydrogen / ethylene = 4.1 × 10 ⁻⁴ , ethylene concentration = 23%).

The yield of the ethylene / 1-hexene copolymer (A-1) thus obtained was 5.6 kg / h, the MFR was 1.4 g / 10 min, and the density was 0.924.
g / cm ³ , and the decane-soluble part at room temperature was 0.08
It was wt%. Ethylene / 1-hexene copolymer (A-
The physical properties of 1) are shown in Table 1.

Preparation of Composition The ethylene copolymer composition was prepared as follows. Dry-blend ethylene / α-olefin copolymer and crystalline polyolefin at a predetermined mixing ratio,
Furthermore, with respect to 100 parts by weight of the resin, tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant is added to 0.2%.
05 wt%, n-octadecyl-3- (4 'as a heat stabilizer
Hydroxy-3 ', 5'-di-t-butylphenyl) propinate was added in an amount of 0.1% by weight, and calcium stearate as a hydrochloric acid absorbent was added in an amount of 0.05% by weight. Then, using a conical taper twin-screw extruder manufactured by Haake Co., set temperature 18
The composition was obtained by kneading at 0 ° C.

[0132]

Reference Example 1 Using the ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1, 20 mmφ · L / D = 26
Air flow rate = 25mmφ die, lip width 0.7mm, single slit air ring
A film having a thickness of 30 μm was extrusion-molded at 90 liters / min., Extrusion rate = 9 g / min., Blow ratio = 1.8, take-up speed = 2.4 m / min., Processing temperature = 200 ° C.

Table 3 shows the melt characteristics and film physical properties.

[0134]

Example 1 The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 and the high-density polyethylene (B-1) shown in Table 2 were used in a weight ratio (A-1) / (B- 1) = 90 /
The mixture was melt-kneaded at 10 to obtain an ethylene-based copolymer composition.
Using this ethylene-based copolymer composition, a film with a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As compared with Reference Example 1, an inflation film having improved flowability (FI) in the high shear region and improved rigidity was obtained.

[0136]

Example 2 The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 and the high-density polyethylene (B-2) shown in Table 2 were used in a weight ratio (A-1) / (B- 2) = 90 /
The mixture was melt-kneaded at 10 to obtain an ethylene-based copolymer composition.
Using this ethylene-based copolymer composition, a film with a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As compared with Reference Example 1, an inflation film having improved flowability (FI) in the high shear region and improved rigidity was obtained.

[0138]

Example 3 The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 and the propylene / butene random copolymer (B-3) shown in Table 2 were used in a weight ratio (A-1). /
(B-3) = 90/10 was melt-kneaded to obtain an ethylene-based copolymer composition. Using this ethylene-based copolymer composition, a film with a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As compared with Reference Example 1, an inflation film having improved flowability (FI) in the high shear region and improved rigidity was obtained.

[0140]

Example 4 The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 and the polypropylene (B-4) shown in Table 2 were used in a weight ratio (A-1) / (B-4). = 90/1
The mixture was melt-kneaded at 0 to obtain an ethylene-based copolymer composition. Using this ethylene-based copolymer composition, a film with a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As compared with Reference Example 1, an inflation film having improved flowability (FI) in the high shear region and improved rigidity was obtained.

[0142]

Example 5 The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 and the polybutene-1 (B shown in Table 2
-5) was melt-kneaded at a weight ratio (A-1) / (B-5) = 90/10 to obtain an ethylene-based copolymer composition. A film having a thickness of 30 μm was formed by inflation molding using this ethylene copolymer composition. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As compared with Reference Example 1, an inflation film having improved flowability (FI) in the high shear region and improved rigidity was obtained.

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Toshiyuki Tsutsui, No. 1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Co., Ltd. (56) Reference JP-A-4-248855 (JP , A) JP-A-60-35008 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08F 4/64-4/69 C08F 210/00 -210/18

Claims (2)

(57) [Claims] 1. [A1] (a) an organoaluminum oxy compound, (b) at least one selected from transition metal compounds represented by the following general formula [I], and ML ¹ _X ... [I] M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand that coordinates with the transition metal atom M, and at least two of these ligands L ¹ are Cyclopentadienyl group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) At least one selected from transition metal compounds represented by the following general formula [II] and ML ² _X ... [II] (wherein M is a transition metal atom selected from Group IVB of the periodic table, and L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among them are substituted cyclopentadiene having only 2 to 3 substituents selected from a methyl group and an ethyl group. The ligand L ^{2 which} is an enyl group other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. In the presence of an olefin polymerization catalyst containing a transition metal compound of Group IV of the periodic table containing at least two kinds of ligands having a cyclopentadienyl skeleton,
-Obtained by copolymerizing with an olefin, (i) the density is in the range of 0.850 to 0.980 g / cm ³ , and (ii) the melt flow rate (MFR) at 190 ° C and a load of 2.16 kg. It is in the range of 0.01 to 200 g / 10 minutes, and (iii) the melt tension (MT) at 190 ° C.
(G)) and the melt flow rate (MFR) satisfy the relationship ^represented by the following formula MT> 2.2 × MFR ^−0.84 , and (iv) the shear stress at 190 ° C. of the melt copolymer is 2.
The fluidity index (FI (1 / sec)) defined by the shear rate when reaching 4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) satisfy the relationship represented by FI <150 × MFR. 60 to 99% by weight of an ethylene / α-olefin copolymer, and [B] 1 to 40% by weight of at least one crystalline polyolefin selected from the following groups (B-I) to (B-III). (B-I) a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg in the range of 0.01 to 100 g / 10 minutes, and a density of 0.900 g. / Cm ³ or more, an ethylene homopolymer, or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms (provided that the ethylene.
(Excluding α-olefin copolymer [A1]) (B-II) Melt flow rate (MFR) at 230 ° C and 2.16 kg load is in the range of 0.1 to 100 g / 10 minutes, and density is 0.900 g. / Cm ³ or more, a propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and α-olefins having 4 to 20 carbon atoms (B-III) 230 ° C, 2.16 kg. Melt flow rate (MFR) under load is in the range of 0.1 to 100 g / 10 minutes, density is more than 0.900 g / cm ³ , homopolymer of α-olefin having 4 to 20 carbon atoms, or carbon number. Copolymers of 4 to 20 α-olefins. 2. From [A2] (a) an organoaluminum oxy compound and (b) a transition metal compound represented by the following general formula [I]:
At least one kind _{^{chosen, ML 1 X ... [I]}} ( wherein M is a transition metal raw selected from Group IVB of the periodic table
A child, L ¹ is Ah in ligand coordinating to the transition metal atom M
Ri, ligand L ¹ at least two of these, sik
Lopentadienyl group, methylcyclopentadienyl group,
Ethyl Le cyclopentadienyl group or 3 to 10 carbon atoms,
Having at least one group of that selected from the group consisting of hydrocarbon radicals
A substituted cyclopentadienyl group, (substituted) cyclopentyl
The ligand L ¹ other than the naphthadienyl group has 1 to 12 carbon atoms.
Hydrocarbon group, alkoxy group, aryloxy group, trial
A silyl group, a halogen atom or a hydrogen atom, and X
Is the valence of the transition metal M. ) Shown by the following general formula [II]
At least one selected from the following transition metal compounds and ML ² _X ... [II] (wherein M is a transition metal precursor selected from Group IVB of the periodic table).
A child, L ² is Ah in ligand coordinating to the transition metal atom
And at least two of these ligands L ² are
2 to 3 substituents selected from the group
A substituted cyclopentadienyl group having a substituted cyclopentadienyl group
Ligand L ² other than pentadienyl group, 1 to 12 carbon atoms
Hydrocarbon groups, alkoxy groups, aryloxy groups , thoria
An alkyl group, a halogen atom or a hydrogen atom,
X is a valence of the transition metals atom M. ) Consisting of less
And a ligand having two cyclopentadienyl skeletons
Containing a transition metal compound of Group IV of the periodic table containing
Ethylene and α having 3 to 20 carbon atoms in the presence of a catalyst for polymerization.
-Obtained by copolymerizing with an olefin, (i) the density is in the range of 0.850 to 0.980 g / cm ³ , and (ii) the melt flow rate (MFR) at 190 ° C and a load of 2.16 kg. It is in the range of 0.01 to 200 g / 10 minutes, and (iii) the melt tension (MT) at 190 ° C.
(G)) and the melt flow rate (MFR) satisfy the relationship ^represented by the following formula MT> 2.2 × MFR ^−0.84 , and (iv) the shear stress at 190 ° C. of the melt copolymer is 2.
The fluidity index (FI (1 / sec)) defined by the shear rate when reaching 4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) satisfy the relationship represented by FI <150 × MFR. , (V) the molecular weight distribution (Mw / Mn) measured by GPC is in the range of 1.5 to 4, (vi) MT / (Mw / Mn) and FI / MFR are MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (However, the value of 0.03 × FI / MFR-3.0 is 0
60 to 99% by weight of an ethylene / α-olefin copolymer satisfying the relationship represented by the following formula: [B] at least one selected from the following groups (B-I) to (B-III) Ethylene-based copolymer composition characterized by comprising 1 to 40% by weight of the crystalline polyolefin; (BI) having a melt flow rate (MFR) of 0.01 to 100 g at 190 ° C. and a load of 2.16 kg. / a 10-minute range, density of more than 0.900 g / cm ^3, ethylene homopolymer, or a copolymer of ethylene and an α- olefin having 3 to 20 carbon atoms (provided that the ethylene
(Excluding α-olefin copolymer [A1]) (B-II) Melt flow rate (MFR) at 230 ° C and 2.16 kg load is in the range of 0.1 to 100 g / 10 minutes, and density is 0.900 g. / Cm ³ or more, a propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and α-olefins having 4 to 20 carbon atoms (B-III) 230 ° C, 2.16 kg. Melt flow rate (MFR) under load is in the range of 0.1 to 100 g / 10 minutes, density is more than 0.900 g / cm ³ , homopolymer of α-olefin having 4 to 20 carbon atoms, or carbon number. Copolymers of 4 to 20 α-olefins.