JPH11322852A - Copolymer of ethylene and alpha-olefin, and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene and α-olefin copolymer excellent in moldability capable of forming a film excellent in transparency and mechanical strength by copolymerizing ethylene and α-olefin. SOLUTION: This copolymer satisfying the following relation is obtained by copolymerizing ethylene and a 6-8C α-olefin: 9.0×MFR<-0.64> >MT >2.2×MFR<-0.84> (MT is melt tension at 190 deg.C, MFR is melt flow rate at the same temperature); [0.039Ln(C-2)+0.0096]×x+2.87<Ea×10<-4> <=[0.039Ln(C-2)+0.1660]×x+2.87 [Ea is the activation energy (Ea×10<-4> J/molK) of the flow calculated from the shift factor of the overlap of the time-temperature of the flow curve,; C is the carbon number of the α-olefin in the copolymer,; (x) the content of the α-olefin in the copolymer (x mol.%)]. This copolymer is preferably obtained by copolymerizing the monomers under the presence of a catalyst for olefin polymerization comprising an organo aluminumoxy compound and a transition metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ethylene / α-olefin copolymer, and more particularly to an ethylene / α-olefin copolymer capable of producing a film having excellent moldability, transparency and mechanical strength. About. The present invention also relates to an ethylene copolymer composition having substantially the same composition and utility as the ethylene / α-olefin copolymer.

[0002] The present invention further relates to a composition of the above-mentioned ethylene / α-olefin copolymer or ethylene-based copolymer composition and another ethylene-based copolymer. Furthermore, the present invention relates to a method for producing the above-mentioned ethylene / α-olefin copolymer.

[0003]

BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The required properties of the ethylene copolymer differ depending on the molding method and application. For example, when molding an inflation film at a high speed, the melt tension (melt tension) of the ethylene-based copolymer is low in order to stably perform the high-speed molding without bubble fluctuation or tearing. You have to choose the big one. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width drop in T-die molding.

A method of improving the moldability by improving the melt tension (melt tension) and expansion ratio (die swell ratio) of an ethylene polymer obtained using a Ziegler catalyst, particularly a titanium catalyst, is disclosed in 56-90810
And Japanese Patent Application Laid-Open No. 60-106806. However, in general, ethylene-based polymers obtained using a titanium-based catalyst, particularly low-density ethylene-based copolymers, have a wide composition distribution and may contain components that cause stickiness when formed into a molded product such as a film. It has been desired to further reduce the components that cause many stickiness.

[0005] Among ethylene polymers produced using a Ziegler-type catalyst, an ethylene polymer obtained using a chromium-based catalyst has a relatively high melt tension, but further thermal stability is expected. Was rare.

[0006] Ethylene copolymers obtained with olefin polymerization catalysts containing transition metal metallocene compounds include:
Many of them have high melt tension and good thermal stability, and are expected to meet the above demands. However, in the case of an ethylene copolymer obtained by using a metallocene catalyst, generally, the melt tension (M
T) and the flow activation energy (Ea) are in a proportional relationship.

As described above, a polymer having a large melt tension has excellent moldability because of its excellent bubble stability. However, the flow activation energy (Ea) is high,
This means that the temperature dependency of the molding conditions is large. For this reason, unless the molding conditions are controlled very strictly and uniformly, unevenness occurs in the obtained molded body.
For example, in the case of a film, transparency may be reduced.

On the other hand, if the flow activation energy (Ea) is low, the occurrence of unevenness in the molded body can be prevented, but the melt tension is low, the bubbles become unstable, and the moldability deteriorates.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to produce a film having excellent transparency and mechanical strength.
It is an object of the present invention to provide an α-olefin copolymer and an ethylene-based copolymer composition having substantially the same composition and utility.

[0010]

The ethylene / α-olefin copolymer (A) according to the present invention is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms, and (A-i) at 190 ° C. Melt tension (MT) and melt flow rate (MFR)
^{Satisfies the} relationship of 9.0 × MFR− ^0.65 >MT> 2.2 × MFR− ^0.84 , and (A-ii) the activation of the flow obtained from the shift factor of the time-temperature superposition of the flow curve. Relationship between energy ((E _a ) × 10 ⁻⁴ J / molK), carbon number (C) of α-olefin in the copolymer, and α-olefin content (x mol%) in the copolymer but, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87 is satisfied, and (A-iii) the copolymer is subjected to inflation molding to produce a film having a thickness of 30 μm. Haze) satisfies the following relationship.

The shear stress at 190 ° C. is 2.4 × 10
Fluidity index (FI) defined by the shear rate when reaching ⁶ dyne / cm ² and melt flow rate (MF)
R) When FI ≧ 100 × MFR When α-olefin has 6 carbon atoms (C), Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) The shear stress at 190 ° C. is 2 .4 × 10 ⁶ dyne / cm
When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when reaching ² are FI <100 × MFR When the number of carbon atoms (C) of the α-olefin is 6, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) (where d is the density ( g / cm ³ ), and MT indicates the melt tension (g).)

The ethylene / α-olefin according to the present invention
The method for producing the polymer (A) is as follows:
Xy compound and (b-I) a compound represented by the following general formula (I)
At least one transition metallization selected from transfer metal compounds
Compound and ML¹ _X ... (I) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L¹Is a ligand that coordinates to the transition metal atom M,
At least two of these ligands L¹Is 3 carbon atoms
At least one group selected from hydrocarbon groups of 10 to 10
A substituted cyclopentadienyl group having
Ligands other than pentadienyl groups L¹Has 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, tria
A rusilsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal M. ) (B-II) The following general
At least one selected from transition metal compounds represented by formula (II)
And one transition metal compound, ML^Two _X ... (II) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L^TwoIs a ligand that coordinates to the transition metal atom M,
At least two of these ligands L^TwoIs methyl
Clopentadienyl group or ethylcyclopentadienyl
A methylcyclopentadienyl group or an ethyl group.
Ligands other than rucyclopentadienyl group L ^TwoIs the carbon number
1 to 12 hydrocarbon groups, alkoxy groups, aryloxy
Group, trialkylsilyl group, halogen atom or hydrogen atom
And X is the valence of the transition metal atom M. From)
Ethylene and carbon in the presence of an olefin polymerization catalyst
By copolymerizing with an α-olefin of the formulas 6 to 8,
It is characterized by being obtained.

In the above-mentioned catalyst, it is preferable that (a) the organoaluminum oxy compound, (b-I) transition metal compound and (b-II) transition metal compound are supported on (c) a carrier.

The ethylene / α-olefin copolymer (A) as described above can produce a film excellent in moldability, transparency and mechanical strength. The ethylene-based copolymer composition (A ′) according to the present invention has substantially the same composition and utility as the above-mentioned ethylene / α-olefin copolymer, and (B) ethylene and C6 to C8. Is a copolymer with an α-olefin having a (Bi) density of 0.880 to
0.970 g / cm ³ , and (B-ii) 190
° C, melt flow rate at 2.16 kg load (M
FR) is in the range of 0.02 to 200 g / 10 minutes, and (B)
-Iii) When the content rate (W) and the density (d) of the decane-soluble component at room temperature are MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d−0.88)) + 0.1 MFR> 10 g At the time of / 10 minutes, the relationship represented by W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1 is satisfied, and (B-iv) differential scanning calorimeter (DSC) is used. The temperature (Tm) and the density (d) at the maximum peak position of the measured endothermic curve satisfy the relationship of Tm <400 × d−248, and (B−v) the melt tension (MT) at 190 ° C. and the melt flow. The rate (MFR) satisfies the relationship of 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84 , and (B-vi) was obtained from the shift factor of the time-temperature superposition of the flow curve. The activation energy of the flow ((E _a ) × 10 ⁻⁴ J / molK), the carbon number (C) of the α-olefin in the copolymer, and the α-olefin in the copolymer Relationship for the content of olefin (x mol%) is, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by (B-vii) GPC is 2.2 <Mw / Mn <3.5, (C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. And (Ci) density is 0.8
(C-ii) in the range of 80 to 0.970 g / cm ^3.
The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.02 to 200 g / 10 minutes, and (C-iii) the decane-soluble component content rate (W) at room temperature and the density (d). When MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp ( -100 (d-0.88)) + 0.1, (C-iv) temperature (Tm) and density (d) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC). ^{Satisfies the} relationship expressed by Tm <400 × d-248, and (C−v) the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) are expressed by MT ≦ 2.2 × MFR− ^0.84 . And an ethylene-α-olefin copolymer to be obtained. Wherein the ratio between the melt flow rate (MFR (C)) and the melt flow rate (MFR (B)) of (B) is 1 <(MFR (C)) / (MFR (B)) ≦ 20. .

The ethylene copolymer composition (A ') of the present invention
In the above, both the ethylene / α-olefin copolymers (B) and (C) are ethylene / hexene-1 copolymers, and (A′-i) the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) satisfies the relationship of 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84 , and (A′-ii) was determined from the shift factor of time-temperature superposition of the flow curve. Activation energy of flow ((E _a ) × 10 ⁻⁴ J / molK) and carbon number (C) of hexene-1 in copolymers (B) and (C)
And the total content (x mol%) of hexene-1 in the copolymers (B) and (C) is (0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≤ (0.039L
n (C-2) +0.1660) × x + 2.87 (A′-iii) When the copolymer composition is blown-molded to produce a 30 μm thick film, Preferably has the following relationship:

Shear stress at 190 ° C. is 2.4 × 10
Fluidity index (FI) defined by the shear rate when reaching ⁶ dyne / cm ² and melt flow rate (MF)
R) When FI ≧ 100 × MFR Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 Shear stress at 190 ° C. is 2.4 × 10 ⁶ dyne / cm
When the fluidity index (FI) defined by the shear rate when reaching ² and the melt flow rate (MFR) are FI <100 × MFR, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 (where d is density (g / cm ³ ), MT is melt tension (g), and C is the number of carbon atoms of hexene-1, that is, “6”).

Further, the ethylene copolymer composition (A ') of the present invention is obtained by (A'-iv) GPC in addition to the requirements of (A'-i) to (A'-iii). Of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / M
n) preferably satisfies 2.0 ≦ Mw / Mn ≦ 2.5.

The ethylene / α-olefin copolymer (A) or the ethylene copolymer composition (A ′) of the present invention further comprises (D) (a) an organoaluminum oxy compound, (b-III) By copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound belonging to Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton Obtained
(D-i) Density is in the range of 0.850 to 0.980 g / cm ³ , (D-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.4 to 8 dl / g. And an ethylene / α-olefin copolymer described in (1).

However, the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (D) are not the same, and the ethylene / α-olefin copolymers (B) and (C) And the ethylene / α-olefin copolymer (D) are not the same.

The process for producing an ethylene / α-olefin copolymer according to the present invention comprises the steps of (a) the organoaluminum oxy compound, (b-I) a transition metal compound, and (b-II) a transition metal compound. Is characterized in that ethylene and an α-olefin having 6 to 8 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst.

[0021]

DETAILED DESCRIPTION OF THE INVENTION The ethylene / α according to the present invention will now be described.
-The olefin copolymer (A), the production method thereof, and the ethylene-based copolymer composition (A ') will be specifically described.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It may be used with the incorporation of coalescence. Ethylene / α-olefin copolymer (A) Ethylene / α-olefin copolymer (A) according to the present invention
Is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. As the α-olefin having 6 to 8 carbon atoms used for the copolymerization with ethylene, a linear α-olefin having no branch is preferable, and specifically, for example, 1-hexene, 1-heptene, 1-octene And
In particular, hexene-1 is preferably used.

The ethylene / α-olefin copolymer (A) according to the present invention has the following properties (Ai) to (A-iii). (A-i) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 minutes)] are 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84, preferably 9.0 ^XMFR-0.65 >MT> ^{2.3xMFR-0.84,} more preferably ^8.5xMFR-0.65 >MT> ^2.5xMFR-0.84 .

The ethylene / α-olefin copolymer having such properties has a high melt tension (MT), and thus has good moldability. The MFR is ASTM
It is measured under the conditions of 190 ° C and 2.16 kg load according to D1238-65T.

The melt tension (MT) is determined by measuring a stress when a molten polymer is stretched at a constant speed. That is, the produced polymer powder is melted and pelletized by a usual method to obtain a measurement sample, and a resin temperature of 1 using an MT measuring device manufactured by Toyo Seiki Seisaku-sho, Ltd.
90 ° C., extrusion speed 15 mm / min, winding speed 10
20m / min, nozzle diameter 2.09mmφ, nozzle length 8m
m. At the time of pelletization, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to the ethylene / α-olefin copolymer in advance, as a heat stabilizer. 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. (A-ii) The activation energy of the flow obtained from the shift factor of the time-temperature superposition of the flow curve ((E
_a ) × 10 ⁻⁴ J / molK), the carbon number (C) of α-olefin in the copolymer, and the content of α-olefin in the copolymer
relationship (x mol%) is, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87 , preferably, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n more preferably (C-2) +0.1500) × x + 2.87, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1300) × x + 2.87 is satisfied.

In order to improve the film formability, it is necessary to increase the melt tension, and it is known that the introduction of long chain branches is effective for that purpose. E _a of long chain branching is not ethylene · alpha-olefin copolymer E _a × 10 ^-4 = (0.03
9Ln (C-2) +0.0096) × x + 2.87. If there is a long-chain branch, E _a becomes large, so E _a × 10 ^-4 > (0.039Ln (C
In the case of -2) +0.0096) × x + 2.87, it is presumed that long-chain branching is present, and the film formability and transparency are improved. On the other hand, if the ^{_{E a × 10 -4> (0.039Ln}} (C-2) +0.1660) × x + 2.87, though excellent in moldability, because the film strength and film transparency is deteriorated, unfavorably.

The flow activation energy (E _a ) can be measured, for example, by referring to “Polymer Experiments, Vol. 9, Thermodynamic Properties I (edited by the Society of Polymer Science, Editor of Polymer Experiments, Kyoritsu Shuppan Co., Ltd., No. 25). ~ are described on page 28) ", the viscoelastic frequency dependence was measured, the time - temperature superposition of the shift factor of the flow activation energy (E _a) is obtained. When the graph of the storage elastic modulus (vertical axis) vs. angular velocity (horizontal axis) measured at a certain reference temperature is fixed, and the data measured at another measurement temperature is moved in parallel to the horizontal axis, the reference temperature data and Overlap (thermo-rheological simplicity). The amount by which the data at each measured temperature is shifted so that it can be superimposed on the data at the reference temperature Log (aT) is the reciprocal of the measured temperature (absolute temperature)
The slope of the line obtained by plotting against 1 / T is 2.30
By multiplying by 3R (R is a gas constant), the activation energy is obtained as a constant independent of temperature.

[0028] Specifically, to measure E _a in the following manner. Using a rheometer RDS-II manufactured by Rheometrics, the angular velocity (ω (rad) of the storage modulus (G ′ (dyne / cm ² ))
/ Sec)) The dispersion was measured. Sample holder is 25mm
Using a φ parallel plate, sample thickness is about 2mm
And Measurement temperature is 130, 170, 200, 230 ° C
G ′ was measured at each temperature in the range of 0.04 ≦ ω ≦ 400. When measuring at 130 ° C., in order to completely melt the crystal, the temperature is raised to 150 ° C. and then 130 ° C.,
It was measured. The amount of distortion was appropriately selected in the range of 2 to 25% so that the torque in the measurement range was detectable and the torque was not exceeded. Superimposing a flow curve of the four temperature conditions as the reference temperature of 130 ° C. after the measurement, from Arrhenius plot of the shift factor seek E _a. The calculation is performed using the analysis software RHIO attached to RDS-II.
This was performed using S. (A-iii) When a film having a thickness of 30 μm is produced from the ethylene / α-olefin copolymer by inflation molding, the haze of the film satisfies the following relationship.

The shear stress at 190 ° C. is 2.4 × 10
Fluidity index (FI) defined by the shear rate when reaching ⁶ dyne / cm ² and melt flow rate (MF)
R) When FI ≧ 100 × MFR When α-olefin has 6 carbon atoms (C), Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) The shear stress at 190 ° C. is 2 .4 × 10 ⁶ dyne / cm
When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when reaching ² are FI <100 × MFR When the number of carbon atoms (C) of the α-olefin is 6, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) (where d is the density ( g / cm ³ ), and MT indicates the melt tension (g).)

The ethylene / α-olefin copolymer satisfying these requirements is excellent in moldability and transparency of the obtained film. The flow index (FI) is used to extrude the resin from the capillary while changing the shear rate,
It is determined by measuring the stress at that time. That is, using the same sample as in the MT measurement, and manufactured by Toyo Seiki Seisakusho,
Using a capillary flow property tester, the resin temperature is measured at 190 ° C., and the shear stress is measured in a range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

The nozzle diameter is changed as follows according to the MFR (g / 10 minutes) of the resin to be measured. 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 The density (d) at 190 ° C. 2. A strand obtained at the time of measuring a melt flow rate (MFR) under a load of 16 kg is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and measured with a density gradient tube.

The ethylene / α-olefin copolymer (A) according to the present invention preferably satisfies the following requirements in addition to the above requirements. In the ethylene / α-olefin copolymer (A) according to the present invention, the constituent unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, and most preferably. Is present in an amount of 70 to 96% by weight, and a structural unit derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, It is particularly preferred that it be present in an amount of 4 to 30% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. 120
° C, measurement frequency 25.05 MHz, spectrum width 150
0 Hz, pulse repetition time 4.2 sec., Pulse width 6 μse
It is determined by measuring under the measurement conditions of c.

Ethylene / α-olefin copolymer (A)
Has a density (d) of 0.880 to 0.970 g / cm ³ ,
Preferably, it is in the range of 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0.935 g / cm ³ , most preferably 0.905 to 0.930 g / cm ³ .

Ethylene / α-olefin copolymer (A)
Has a melt flow rate (MFR) of 0.02 to 200
g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

Ethylene / α-olefin copolymer (A)
When the fraction of the n-decane soluble component at 23 ° C. [W (% by weight)] and the density [d (g / cm ³ )] are MFR ≦ 10 g / 10 minutes, W <80 × exp (-100) (d-0.88)) + 0.1 preferably W <60 × exp (-100 (d-0.88)) + 0.1, more preferably W <40 × exp (-100 (d-0.88)) + 0.1 MFR> 10 g / 10 In the case of minutes, it is desirable that the relationship represented by W <80 × (MFR-9) ^0.26 × exp (-100 (d−0.88)) + 0.1 is satisfied.

The ethylene / α-olefin copolymer
The amount of the n-decane soluble component (the smaller the amount of the soluble component, the narrower the composition distribution) is measured by measuring about 3 g of the copolymer with n-decane 450.
After dissolving at 145 ° C, the solution is cooled to 23 ° C, the n-decane-insoluble portion is removed by filtration, and the n-decane-soluble portion is recovered from the filtrate.

Ethylene / α-olefin copolymer (A)
Temperature [Tm (° C.)] and density [d (g) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC).
/ Cm ³ )] It is desirable to satisfy the relationship shown by.

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) was measured by placing about 5 mg of a sample in an aluminum pan, heating to 200 ° C. at 10 ° C./min. , The temperature is lowered to room temperature at 20 ° C / min, and then the temperature is increased at 10 ° C / min. The measurement was made by PerkinElmer DS
Use C-7 type equipment.

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

In the present invention, the ethylene
The α-olefin copolymer (A) can be used in combination of two or more kinds. The ethylene / α-olefin copolymer (A) according to the present invention comprises at least one selected from (a) an organoaluminum oxy compound and (b-I) a transition metal compound represented by the general formula (I). Of an olefin polymerization catalyst (Cat-1) formed from a transition metal compound represented by the formula (b-II) and at least one transition metal compound selected from the transition metal compounds represented by the general formula (II): It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms below.

In the above, (a) an organoaluminum oxy compound, (b-I) at least one transition metal compound selected from the transition metal compounds represented by formula (I), and (b-II) At least one transition metal compound selected from the transition metal compounds represented by (II) may be supported on a carrier (c) (hereinafter, such a supported catalyst is abbreviated as Cat-2. There is).

First, the respective catalyst components forming the olefin polymerization catalysts (Cat-1) and (Cat-2) will be described. (A) Organic aluminum oxy compound The organic aluminum oxy compound (a) used in the present invention (hereinafter sometimes referred to as “component (a)”).
May be a conventionally known benzene-soluble aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound as disclosed in JP-A-2-276807.

The aluminoxane as described above can be produced, for example, by the following method and is usually obtained as a hydrocarbon solution. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react.

(2) A method in which water, ice or steam is allowed to act directly 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 an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in producing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-aluminum.
Trialkylaluminum such as butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dimethylaluminum methoxide, diethylaluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. 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) Isoprenyl aluminum can also be used.

The organoaluminum compound as described above is
Used alone or in combination. As a 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 and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum distillates such as gasoline, kerosene and light oil And hydrocarbon solvents such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon halides (eg, chlorinated products, brominated products, etc.). In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is such that the organoaluminum oxy compound corresponding to 100 milligram atoms of Al is 10
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

(B-I) Transition metal compound and (b-II)
Transition metal compound The transition metal compound (b-I) used in the present invention is a transition metal compound represented by the following general formula (I), and the transition metal compound (b-II) is represented by the following general formula (II). The transition metal compound represented.

ML¹ _X ... (I) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L¹Is a ligand that coordinates to the transition metal atom M,
At least two of these ligands L¹Is 3 carbon atoms
At least one group selected from hydrocarbon groups of 10 to 10
A substituted cyclopentadienyl group having
Ligands other than pentadienyl groups L¹Has 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, tria
A rusilsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) ML^Two _X ... (II) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L^TwoIs a ligand that coordinates to the transition metal atom M,
At least two of these ligands L^TwoIs methyl
Clopentadienyl group or ethylcyclopentadienyl
A methylcyclopentadienyl group or an ethyl group.
Ligands other than rucyclopentadienyl group L ^TwoIs the carbon number
1 to 12 hydrocarbon groups, alkoxy groups, aryloxy
Group, trialkylsilyl group, halogen atom or hydrogen atom
And X is the valence of the transition metal atom M. Hereinafter, the transition represented by the above general formula (I) or (II)
The metal compound will be described more specifically.

In the above general formula (I), M is a transition metal atom selected from Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and 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 hydrocarbon groups having 3 to 10 carbon atoms
A substituted cyclopentadienyl group having various substituents. These ligands L ¹ may be the same or different.

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 may be a methyl group or 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, such as decyl group Alkyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group and neophyl group.

Of these, alkyl groups are preferred, and n-propyl and n-butyl groups are particularly preferred. In the present invention, the substituted cyclopentadienyl group coordinated to the transition metal is preferably a disubstituted cyclopentadienyl group, and particularly preferably a 1,3-substituted cyclopentadienyl group.

In the 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, an aryloxy group. , A trialkylsilyl group, a halogen atom 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 an n-propyl group. Groups, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and other alkyl groups; cyclopentyl group, cyclohexyl group, etc. A phenyl group,
Examples include an aryl group such as a tolyl group; and an aralkyl group such as a benzyl group and a neophyl group.

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

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 (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-
Hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl)
Zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n -Butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxycyclolide, 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-butylcyclopentadienyl) zirconium hydride chloride and the like.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted 1,2-, 3- and 1,2,4- Including substitutions. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the zirconium compound as described above can be used.

Among the 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 fourth term in the periodic table.
A transition metal atom selected from the group, specifically, zirconium, titanium or hafnium, and preferably zirconium.

L ² is a ligand coordinated to the transition metal atom M, and at least two of the ligands L ² are a methylcyclopentadienyl group or an ethylcyclopentadienyl group; Each may be the same or different.

In the general formula (II), the ligand L ² other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group coordinated to the transition metal atom M is represented by the general formula (I) L ¹ and similar hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

As the transition metal compound represented by the general formula (II), bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) Zirconium dibromide, bis (ethylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium methoxychloride, bis (ethylcyclopentadienyl) zirconium methoxychloride, bis (methylcyclopentadienyl) zirconium ethoxy Chloride, bis (ethylcyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium diethoxide, bis (ethylcyclopentadienyl) zirconiumdioxide Toxide, bis (methylcyclopentadienyl) zirconium methyl chloride, bis (ethylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis ( Methylcyclopentadienyl) zirconium benzyl chloride, bis (ethylcyclopentadienyl) zirconium benzyl chloride, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (ethylcyclopentadienyl) zirconium dibenzyl, bis (methylcyclo (Pentadienyl) zirconium phenyl chloride, bis (ethylcyclopentadienyl) zirconium phenyl chloride, bis (methylcyclopentadienyl) zirconium Examples include idride chloride and bis (ethylcyclopentadienyl) zirconium hydride chloride.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the zirconium compound as described above can be used.

Among the transition metal compounds represented by the general formula (II), bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride are particularly preferred.

In the present invention, as the transition metal compound, at least one transition metal compound selected from the transition metal compounds represented by the above general formula (I) and the transition metal compound represented by the above general formula (II) are used. At least one selected transition metal compound is used in combination. As a combination method, the MFR (MFR (I)) of an olefin polymer obtained from a catalyst component containing only the transition metal compound represented by the above general formula (I) as a transition metal compound component under the same polymerization conditions is used. The MFR of the olefin polymer obtained from the catalyst component containing only the transition metal compound represented by the general formula (II) as the transition metal compound component (MFR
FR (II)) is MFR (I) / MFR (II) ≦ 2
It is preferable to use a combination of catalysts that becomes zero.

Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propylmethyl) A combination of (cyclopentadienyl) zirconium dichloride with bis (methylcyclopentadienyl) zirconium dichloride and a combination of bis (n-butylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride are preferred. .

At least one transition metal compound selected from the transition metal compounds represented by the general formula (I) (b-
I) and at least one transition metal compound (b-II) selected from the transition metal compounds represented by the general formula (II) are in a molar ratio (bI / b-II) of 99/1 to 40. / 60, preferably 95/5 to 45/55, more preferably 90 /
10/50/50, most preferably 85 / 15-55 /
It is desirable that the amount be used so as to fall within the range of 45.

Hereinafter, at least one selected from the transition metal compounds (bI) represented by the above general formula (I) and at least one selected from the transition metal compounds (b-II) represented by the above general formula (II) The transition metal compound catalyst component containing at least one component may be referred to as “component (b)”.

The olefin polymerization catalyst (Cat
-1) is the above-mentioned organoaluminum oxy compound (a), transition metal compound (b-I) and transition metal compound (b-II)
Which is formed from the following carrier (c):
The above organoaluminum oxy compound (a), transition metal compound (b-I), and transition metal compound (b-II) can be supported and used as a catalyst (Cat-2).

(C) Carrier The (c) carrier optionally used in the present invention is an inorganic or organic compound having a particle size of 10 to 300 μm.
m, preferably 20 to 200 μm, in the form of granules or fine particles. Of these, a porous oxide is preferable as the inorganic compound, and specifically, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, Z
nO, BaO, ThO ₂ or the like or a mixture containing these,
For example, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -T
iO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO _2-
TiO ₂ -MgO and the like can be exemplified.

Of these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as the main component are preferred. In addition, 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 (N
O ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, etc. may contain carbonate, sulfate, nitrate and oxide components.

The nature of the carrier (c) varies depending on the kind and the 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. , Pore volume is 0.3 ~
Desirably, it is 2.5 cm ³ / g. The carrier is, if necessary, 100-1000 ° C., preferably 150-7 ° C.
It is used by firing at 00 ° C.

In such a carrier (c), the amount of adsorbed water is desirably less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl groups are 1.0% by weight or more, preferably 1.0% by weight or more. 5 to 4.0% by weight, particularly preferably 2.0 to
It is desirably 3.5% by weight.

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] at a temperature of 200 ° C. under normal pressure and nitrogen flow
The percentage of the weight loss after drying for a time relative to the weight before drying is defined as the amount of adsorbed water.

[Amount of Surface Hydroxyl Group] The weight of the carrier obtained by drying at 200 ° C. for 4 hours under a normal pressure under nitrogen flow is defined as X (g), and the carrier is calcined at 1000 ° C. for 20 hours. Of the calcined product from which the surface hydroxyl groups have disappeared
(G) is calculated by the following equation.

Surface hydroxyl group content (% by weight) = {(XY) / X} × 100 Further, as the carrier (c) that can be used in the present invention, an organic compound having a particle size in the range of 10 to 300 μm is used. And granular or fine solid particles. These organic compounds include α, having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
-(Co) polymers mainly composed of olefins or polymers or copolymers mainly composed of vinylcyclohexane and styrene can be exemplified.

Further, the following organoaluminum compound (d) can be used as necessary as a component for forming the olefin polymerization catalysts (Cat-1) and (Cat-2) according to the present invention.

(D) Organoaluminum Compound The (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) used as necessary in the present invention includes, for example, the following general formula (i) The organic aluminum compound represented by these can be illustrated.

R ¹ _n AlX _3-n (i) (wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms;
Is a halogen atom or a hydrogen atom, and n is 1 to 3. In the general formula (i), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound (d) include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (d), a compound represented by the following general formula (ii) can also be used. R ¹ _n AlY _3-n (ii) (wherein, R ¹ is the same as above, Y is —OR ² group,
OSiR ³ ₃ groups, -OAlR ⁴ ₂ groups, -NR ⁵ ₂ groups, -S
iR ⁶ ₃ group or -N (R ⁷⁾ is AlR ⁸ ₂ group, n represents 1
And R ² , R ³ , R ⁴ and R ⁸ are a methyl group,
R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, or the like; R ⁶ and R ⁷ are a methyl group; an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, and a phenyl group; ,
And an ethyl group. ) Specific examples of such an organoaluminum compound include the following compounds. _{^{(1) R 1 n Al (}} OR 2) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R 1 n Al}} (OSiR 3 3) 3 a compound represented by _-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
_{(OSiMe 3), (iso-} Bu) 2 Al (OSiEt 3) , _{^{etc.; (3) R 1 n Al}} (OAlR 4 2) a compound represented by _3-n,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
l (iso-Bu) _{2, ^{etc.; (4) R 1 n Al}} (NR 5 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlN
HEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ Al
N etc. _{(SiMe 3) 2; (5} ) R 1 n Al (SiR 6 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} ; (6) R 1 n Al (N ( R ⁷⁾ AlR ⁸ ₂₎ a compound represented by _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , (iso-B
u) ₂ AlN (Et) Al (iso-Bu) ₂ etc.

[0090] Among the organic aluminum compounds represented by the general formula (i) and (ii), the general formula R ¹ ₃ Al,
_{^{R 1 n Al (OR 2)}} 3-n, R 1 n Al (OAlR 4 2) 3-n
The compound represented by is preferred, and particularly the compound wherein R ¹ is an isoalkyl group and n = 2 is preferred.

The olefin polymerization catalyst (Cat-1) is formed from the components (a) and (b) as described above and, if necessary, the component (d).
(Cat-2) (solid catalyst (Cat-2)) comprises a solid catalyst (component) comprising the above-mentioned component (a) and component (b) supported on a carrier (c), and optionally a component (D).

FIG. 1 shows a process for preparing an olefin polymerization catalyst (Cat-1). The catalyst for olefin polymerization (Cat-1) can be prepared by mixing and contacting each catalyst component in a polymerization vessel or outside the polymerization vessel. After converting component (a) into a solid component, component (b) Can be mixed and contacted to form a solid catalyst, or the components (a) and (b) can be mixed and contacted in advance to form a solid catalyst, and then the solid catalyst can be added to the polymerization system. .

The olefin polymerization catalyst (Cat-1) can be formed by mixing and contacting the components (a) and (b) and, if necessary, the component (d) in an inert hydrocarbon solvent. . The order of contact of the components is arbitrarily selected, but when the components (a) and (b) are mixed and contacted,
Preferably, component (b) is added to the suspension of component (a). The component (b) is composed of two or more transition metal compounds forming the component (b) (components (b-I) and (b-II))
Is preferably mixed and then brought into contact with other components.

Specific examples of the inert hydrocarbon solvent used for preparing the catalyst for olefin polymerization (Cat-1) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene. Hydrogen; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof. be able to.

When the component (a), the component (b) and, if necessary, the component (d) are mixed and contacted, the concentration of the component (a) is about 0.1% in terms of aluminum in the component (a).
-5 mol / l (solvent), preferably 0.3-3 mol / l (solvent). The atomic ratio (Al / transition metal) of aluminum (Al) in the component (a) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a) used as required.
a) is usually 0.02 to 3, preferably 0.05 to 1.
5 range. The mixing temperature at the time of mixing and contacting the component (a), the component (b) and, if necessary, the component (d) is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 minute. ~ 50 hours, preferably 10 minutes ~ 2
5 hours.

The olefin polymerization catalyst (Cat-1) prepared as described above contains the component (b) in an amount of 5 × 10 ^{-6 to} 5 × 10 ^-4 mol in terms of transition metal atom per gram of the catalyst. , Preferably in an amount of 10 ^{-5 to} 2 × 10 ^-4 mol, and the component (a) and the component (d) are preferably 10 ^{−2 to} 2.5 × 10 ^-2 mol, preferably in terms of aluminum atom. Is 1.5 × 1
It is desirable to contain it in an amount of 0 ^{-2 to} 2 × 10 ^-2 mol.

The solid catalyst (Cat-2) comprises the above components (a) and (b), and if necessary, component (d),
It can be prepared by being supported on a carrier (c). The order of contacting the component (a), the component (b), the carrier (c) and the component (d) when preparing the solid catalyst (Cat-2) can be arbitrarily selected, but preferably the component (a) and the carrier (C) is mixed and contacted, then the component (b) is mixed and contacted, and if necessary, the component (d) is mixed and contacted. The component (b) is obtained by mixing two or more transition metal compounds forming the component (b), components (b-I) and (b-II)) in advance, and then mixing and contacting with other components. Is preferred.

The above component (a), component (b), carrier (c)
And the component (d) can be contacted in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon solvent used for preparing the catalyst include the above-mentioned olefin polymerization catalyst (C
The inert hydrocarbon solvent used in the preparation of at-1) can be mentioned.

Upon mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d), the component (b) is converted into transition metal atoms per 1 g of the carrier (c). And is usually used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, and the component (b)
Is in the range of about 10 ^-4 to 2 × 10 ^-2 mol / l (solvent), preferably 2 × 10 ^-4 to 10 ^-2 mol / l (solvent). Atomic ratio of aluminum (Al) in component (a) to transition metal in component (b) (Al /
Transition metal) is usually 10 to 500, preferably 20 to 2
00. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a) used as required is usually 0.1. The range is from 02 to 3, preferably from 0.05 to 1.5. The mixing temperature at the time of mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d) is usually -50 to 150 ° C, preferably -20 to 120 ° C, The contact time is 1 minute to 50 hours, preferably 10 minutes to 2 hours.
5 hours.

The solid catalyst prepared as described above (Cat
Component (b) is 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 1 mol / g of the component (b) in terms of transition metal atom per 1 g of the carrier (c).
The carrier (c) is supported in an amount of 0 ^{-5 to} 2 × 10 ^-4 mol.
Component (a) and component (d) are converted to aluminum atoms in an amount of 10 ^{−3 to} 5 × 10 ⁻² mol, preferably 2 ×, per 1 g.
It is desirable to be supported in an amount of 10 ^{-3 to} 2 × 10 ^-2 mol.

The olefin polymerization catalyst (Cat-
2) may be a prepolymerized catalyst obtained by prepolymerizing an olefin. The prepolymerization catalyst can be prepared by introducing an olefin into an inert hydrocarbon solvent and performing prepolymerization in the presence of the components (a), (b) and the carrier (c). Preferably, the solid catalyst component (Cat-2) is formed from the above component (a), component (b) and carrier (c). In this case, the solid catalyst component (Cat
In addition to -2), component (a) and / or component (d) may be further added.

The prepolymerized catalyst is the above-mentioned solid catalyst (Cat-2)
An olefin may be introduced into the suspension in which the (solid catalyst component) is prepared, and after the solid catalyst (Cat-2) is prepared, the produced solid catalyst (Cat-2) is separated from the suspension, Thereafter, the solid catalyst (Cat-2) may be suspended again with an inert hydrocarbon, and olefin may be introduced therein.

In preparing the prepolymerized catalyst, the above component (b) is usually used in an amount of 10 ⁻⁶ to 2 × 10 ⁻² mol / l (solvent) in terms of transition metal atoms in the component (b). The solvent is used in an amount of preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / l (solvent), and the component (b) is usually 5 × 10 ⁻⁶ to 1 g of the carrier (c) in terms of transition metal atoms. It is used in an amount of 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. The atomic ratio (Al / transition metal) of aluminum in the component (a) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. Aluminum atom (Al-d) in component (d) and component (a) used as required
Atomic ratio (Al-d / Al-) of aluminum atoms (Al-a)
a) is usually 0.02 to 3, preferably 0.05 to 1.
5 range.

The solid catalyst component is usually 10 ^-6 to 2 × 10 ^-2 mol / l (solvent), preferably 5 × 10 ^-5 to 10 ^-2 mol / l (solvent) as a transition metal in the transition metal compound. Used in amounts.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hour, preferably about 1 to 50 hours. As the olefin used in the prepolymerization, ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and the like can be exemplified. Among them, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferred.

The prepolymerization catalyst is prepared, for example, as follows. That is, the carrier is suspended with an inert hydrocarbon. Next, an organic aluminum oxy compound (component (a)) is added to the suspension and reacted for a predetermined time.
Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. After adding a transition metal compound (component (b)) to the system and reacting for a predetermined time, the supernatant is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduced therein to obtain a prepolymerized catalyst.

In the prepolymerization, the produced olefin polymer is used in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g per 1 g of the carrier (c).
Desirably, the amount is g.

In the case of the prepolymerized catalyst, 1 g of the carrier (c) was used.
The hit component (b) is about 5 × 10 ⁻⁶ in terms of transition metal atoms.
５5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, and the aluminum atom (Al) in component (a) and component (d) is It is desirable that the compound is supported in a molar ratio (Al / M) to the transition metal atom (M) of 5 to 200, preferably 10 to 150.

The prepolymerization can be carried out either in a batch system or a continuous system, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Intrinsic viscosity [η] measured in decalin at least 135 ° C. in the coexistence of hydrogen in the range of 0.2 to 7 dl / g;
It is desirable to produce a prepolymer of preferably 0.5 to 5 dl / g.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the presence of the above-mentioned catalyst for olefin polymerization in the gas phase or in the slurry liquid phase, preferably in the gas phase. . In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a 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, 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. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

When the polymerization is carried out by the slurry polymerization method or the gas phase polymerization method, the above-mentioned catalyst is usually used in a concentration of 10 ^-8 to 10 ^-3 mol / l, preferably 10 ^-8 to 10 ^-3 mol / l, in the polymerization reaction system. Is preferably used in an amount of 10 ^-7 to 10 ^-4 mol / l.

In the olefin polymerization catalyst formed from the components (a) and (b) and, if necessary, the component (d), the aluminum atom (Al) in the component (d) used as required And the atomic ratio (Al / M) of the transition metal atom (M) in the transition metal compound (b) is 5 to 30.
0, preferably 10 to 200, more preferably 15 to 1
The range is 50.

In the case of an olefin polymerization catalyst formed of component (a), component (b), carrier (c) and, if necessary, component (d), the organic aluminum oxide In addition to the compound (component (a)), an unsupported organoaluminum oxy compound may be used. In this case, the atomic ratio (Al / M) between the aluminum atom (Al) in the unsupported organoaluminum oxy compound and the transition metal atom (M) in the transition metal compound (b) is 5 to 300,
Preferably 10 to 200, more preferably 15 to 150
Range. The component (d) used as necessary may be supported on the carrier (c), or may be added during polymerization. Further, the component (d) is supported on the carrier (c),
Further, it may be added at the time of polymerization. At this time, the component (d) supported on the carrier and the component (d) added during the polymerization are added.
May be the same or different. An aluminum atom (Al) in the component (d) optionally used;
The atomic ratio (Al / M) to the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably 10 to 20.
0, more preferably 15 to 150.

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

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

Further, the polymerization can be carried out in two or more stages having different reaction conditions. In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

Examples of olefins that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 6 to 8 carbon atoms, in addition to propylene, 1-butene, 1-pentene and 4-methyl. Α-olefins such as 1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cyclic olefins having 3 to 20 carbon atoms such as cyclopentene and cycloheptene; Norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

In the ethylene / α-olefin copolymer obtained by the olefin polymerization method of the present invention, the constituent unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 99% by weight. From about 98% by weight, most preferably from 70 to 96% by weight, wherein the structural unit derived from the C-C8 alpha-olefin is 0%
Desirably, it is present in an amount of from about 50% by weight, preferably from 1 to 45% by weight, more preferably from 2 to 35% by weight, and most preferably from 4 to 30% by weight.

The ethylene / α-olefin copolymer thus obtained is preferably (Ai) to (A-
A film having the characteristics shown in iii), excellent in moldability, excellent in transparency and mechanical strength can be produced. Ethylene-based copolymer composition (A ′) The ethylene-based copolymer composition (A ′) according to the present invention has substantially the same composition and usefulness as the above-mentioned ethylene / α-olefin copolymer (A). And comprises an ethylene / α-olefin copolymer (B) and a different ethylene / α-olefin copolymer (C).

Ethylene / α-olefin copolymer (B)
Is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. Examples of the α-olefin having 6 to 8 carbon atoms include the same as described above.

Ethylene / α-olefin copolymer (B)
Then, the structural unit derived from ethylene is 50 to 100
% By weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight, and the structural unit derived from the α-olefin having 6 to 8 carbon atoms is 0%. 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably 4% by weight.
Desirably it is present in an amount of up to 30% by weight.

Ethylene / α-olefin copolymer (B)
Preferably has the following characteristics (Bi) to (B-vii), and the following (Bi) to (B-vii)
It is particularly preferred to have the characteristics as shown in ii).

(Bi) The density (d) is 0.880 to
0.970 g / cm ³ , preferably 0.880 to 0.9
60 g / cm ³ , more preferably 0.890 to 0.93
5 g / cm ³ , most preferably 0.905 to 0.930
g / cm ³ .

(B-ii) Melt flow rate (MFR)
Is from 0.02 to 200 g / 10 min, preferably from 0.05 to 200 g / 10 min.
It is in the range of 50 g / 10 min, more preferably 0.1 to 10 g / 10 min.

(B-iii) n-decane soluble component fraction at 23 ° C. [W (% by weight)] and density [d (g / cm ³ )]
When MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d-0.88)) + 0.1, preferably W <60 × exp (-100 (d-0.88)) + 0.1, more preferably W < 40 × exp (-100 (d-0.88)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1 Meets

(B-iv) Temperature at maximum peak position of endothermic curve measured by differential scanning calorimeter (DSC) [Tm
(° C.)] and the density [d (g / cm ³ )] Satisfies the relationship indicated by.

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

(Bv) Melt tension [MT
(G)] and melt flow rate [MFR (g / 10 min)]
And 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84, preferably 9.0 × MFR ^-0.65 >MT> 2.3 × MFR ^{-0.84, and} more preferably 8.5 × MFR ^-0.65 > MT > 2.5 × MFR ^-0.84 .

The ethylene / α-olefin copolymer having such properties has a high melt tension (MT), and thus has good moldability. (B-vi) Flow activation energy ((E _a )) determined from the shift factor of time-temperature superposition of the flow curve
× 10 ^-4 J / molK), the carbon number (C) of α-olefin in the copolymer, and the content of α-olefin in the copolymer
relationship (x mol%) is, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87 , preferably, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n more preferably (C-2) +0.1500) × x + 2.87, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1300) × x + 2.87 is satisfied.

(B-vii) The molecular weight distribution (Mw / Mn, where Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC is 2.2 <Mw / Mn <3.5, preferably 2.4 < It is in the range of Mw / Mn <3.0.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore. The separation column is TSK GNH HT,
The column size is 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 BHT was used as an antioxidant.
(Takeda Pharmaceutical Co., Ltd.) The sample was moved at 1.0 ml / min using 0.025% by weight, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliter, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight Mw <10.
For 00 and Mw> 4 × 10 ⁶ , manufactured by Tosoh Corporation, and for 1000 <Mw <4 × 10 ⁶ , manufactured by Pressure Chemical Company.

(B-viii) The number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms, and less than 1 per polymer molecule. In addition, the quantification of the unsaturated bond is performed by using ¹³ C-NMR, a signal belonging to a group other than the double bond, that is, a signal in a range of 10 to 50 ppm,
And the signal assigned to the double bond, ie 105-15
The area intensity of the signal in the range of 0 ppm is determined from the integral curve and is determined from the ratio.

Ethylene / α-olefin copolymer (B)
Is, for example, (a) an organic aluminum oxy compound,
(B-II) It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms in the presence of an olefin polymerization catalyst containing the transition metal compound represented by the general formula (II). The (a) organic aluminum oxy compound and (b-II) transition metal compound are the same as those described in the method for producing the ethylene / α-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used, or prepolymerization may be performed. The amounts of the components used, the prepolymerization conditions and the main polymerization conditions are the same as in the case of producing the ethylene / α-olefin copolymer (A).

Ethylene / α-olefin copolymer (C)
Is a random copolymer with an α-olefin having 6 to 8 carbon atoms. Examples of the α-olefin having 6 to 8 carbon atoms include the same as described above.

In the ethylene / α-olefin copolymer (C) used in the present invention, the constituent unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight. %, Most preferably from 70 to 96% by weight, wherein the constituent units derived from C6-8 alpha-olefins are from 0 to 50% by weight, preferably from 1 to 45% by weight, more preferably from 2 to 45% by weight. Desirably it is present in an amount of 35% by weight, particularly preferably 4 to 30% by weight.

Ethylene / α-olefin copolymer (C)
Preferably has the following characteristics (Ci) to (Cv), and the following (Ci) to (C-vi)
It is particularly preferable to have the characteristics shown in (1).

(Ci) The density (d) is 0.880 to
0.970 g / cm ³ , preferably 0.880 to 0.9
60 g / cm ³ , more preferably 0.890 to 0.93
5 g / cm ³ , most preferably 0.905 to 0.930
g / cm ³ .

(C-ii) Melt flow rate (MFR)
Is from 0.02 to 200 g / 10 min, preferably from 0.05 to 200 g / 10 min.
It is in the range of 50 g / 10 min, more preferably 0.1 to 10 g / 10 min.

(C-iii) n-decane soluble component fraction at 23 ° C. [W (% by weight)] and density [d (g / cm ³ )]
When MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d-0.88)) + 0.1, preferably W <60 × exp (-100 (d-0.88)) + 0.1, more preferably W < 40 × exp (-100 (d-0.88)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1 Meets

(C-iv) Temperature at maximum peak position of endothermic curve measured by differential scanning calorimeter (DSC) [Tm
(° C.)] and the density [d (g / cm ³ )] Satisfies the relationship indicated by.

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

(Cv) Melt tension [MT
(G)] and melt flow rate [MFR (g / 10 min)]
^{Satisfy the} relationship of MT ≦ 2.2 × MFR− ^0.84 .

(C-vi) The number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms and less than 1 per polymer molecule. Such ethylene
The α-olefin copolymer (C) includes, for example, (a) an organoaluminum oxy compound, (b-I) the above-mentioned general formula (I)
The copolymer is obtained by copolymerizing ethylene and an olefin having 6 to 8 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the following formula: The (a) organic aluminum oxy compound and (b-I) transition metal compound are the same as those described in the method for producing the ethylene / α-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used, or prepolymerization may be performed. The amounts of the components used, the prepolymerization conditions and the main polymerization conditions are the same as in the case of producing the ethylene / α-olefin copolymer (A).

The ethylene copolymer composition (A ′) according to the present invention contains the ethylene / α-olefin copolymer (B) in an amount of 1 to 90% by weight, preferably 2 to 80% by weight. And ethylene-α-olefin copolymer (C)
Is desirably contained in an amount of 10 to 99% by weight, preferably 20 to 98% by weight.

In the ethylene copolymer composition (A ′) comprising the ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C), ethylene / α-olefin A melt flow rate (MFR (B)) of the olefin copolymer (B) and a melt flow rate (MFR) of the ethylene / α-olefin copolymer (C).
It is preferable that the ratio to (C)) is 1 <(MFR (C)) / (MFR (B)) ≦ 20.

In particular, in the present invention, the ethylene.α
-Both the olefin copolymers (B) and (C) are preferably ethylene / hexene-1 copolymers. In this case, the ethylene copolymer composition (A ′) preferably has substantially the same physical properties as the ethylene / α-olefin copolymer (A) as shown below, and has the same usefulness. Be expected. (A'-i) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 min)] are 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84, preferably 9. 0 × MFR− ^0.65 >MT> 2.3 × MFR− ^0.84, more preferably 8.5 × MFR− ^0.65 >MT> 2.5 × MFR− ^0.84 .

The ethylene copolymer composition (A ′) having such properties has a high melt tension (MT), and thus has good moldability. (A'-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) obtained from the shift factor of time-temperature superposition of the flow curve, and copolymers (B) and (C) And the total content of hexene-1 in the copolymers (B) and (C) (xmo
relationship l%) is, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87 , preferably, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n more preferably (C-2) +0.1500) × x + 2.87, (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 -4 ≦ (0.039L
n (C-2) +0.1300) × x + 2.87 is satisfied. (A′-iii) The ethylene-based copolymer composition (A ′)
When a film having a thickness of 30 μm is produced by inflation molding, the haze of the film satisfies the following relationship.

The shear stress at 190 ° C. is 2.4 × 10
Fluidity index (FI) defined by the shear rate when reaching ⁶ dyne / cm ² and melt flow rate (MF)
R) When FI ≧ 100 × MFR Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 Shear stress at 190 ° C. is 2.4 × 10 ⁶ dyne / cm
When the fluidity index (FI) defined by the shear rate when reaching ² and the melt flow rate (MFR) are FI <100 × MFR, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 (where d is density (g / cm ³ ), M
T indicates the melt tension (g), and C indicates the number of carbon atoms of hexene-1, that is, "6". ).

The ethylene copolymer composition (A ′) satisfying these requirements is excellent in moldability and transparency of the obtained film. The ethylene copolymer composition (A ') according to the present invention preferably satisfies the following requirements in addition to the above requirements. (A′-iv) Molecular weight distribution measured by GPC (Mw / M
n, where Mw: weight average molecular weight, Mn: number average molecular weight) is in the range of 2.0 ≦ Mw / Mn ≦ 2.5, preferably 2.0 ≦ Mw / Mn ≦ 2.4.

Further, in the ethylene copolymer composition (A ′) according to the present invention, the constituent unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight. 0 to 50% by weight, preferably 1 to 45% by weight, of a structural unit derived from an α-olefin having 6 to 8 carbon atoms, preferably hexene-1. %, More preferably from 2 to 35% by weight, particularly preferably from 4 to 30% by weight.

The density (d) of the ethylene copolymer composition (A ′) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , and more preferably 0.1 to 0.960 g / cm ³ . It is desirably in the range of 890 to 0.935 g / cm ³ , most preferably 0.905 to 0.930 g / cm ³ .

The melt flow rate (MFR) of the ethylene copolymer composition (A ′) is from 0.05 to 200 g / 10
Min, preferably 0.08 to 50 g / 10 min, more preferably 0.1 to 10 g / 10 min.

23 of the ethylene copolymer composition (A ′)
When the fraction of the n-decane-soluble component [W (% by weight)] and the density [d (g / cm ³ )] at M ° C are MFR ≦ 10 g / 10 minutes, W <80 × exp (−100 (d -0.88)) + 0.1 preferably W <60 × exp (-100 (d-0.88)) + 0.1, more preferably W <40 × exp (-100 (d-0.88)) + 0.1 MFR> 10 g / 10 min When W <80 × (MFR-9) ^0.26 × exp (-100 (d−0.88)) + 0.1 is preferably satisfied.

The temperature [Tm (° C.)] and the density [d (g / cm) at the maximum peak position of the endothermic curve of the ethylene copolymer composition (A ′) measured by a differential scanning calorimeter (DSC).
³ )] It is desirable to satisfy the relationship shown by.

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

Ethylene / α-olefin copolymer (B)
And an ethylene-α-olefin copolymer (C) can be produced by using a known method, for example, by the following method. Can be manufactured.

(1) An ethylene / α-olefin copolymer (B) and an ethylene / α-olefin copolymer (C)
And a method of mechanically blending or melt-mixing other components to be added as required using a tumbler, an extruder, a kneader or the like.

(2) Ethylene / α-olefin copolymer (B) and ethylene / α-olefin copolymer (C)
And optionally other components added to a suitable good solvent (eg, hexane, heptane, decane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene and xylene)
And then removing the solvent.

(3) An ethylene / α-olefin copolymer (B) and an ethylene / α-olefin copolymer (C)
And a method in which other components to be added as required are separately dissolved in a suitable good solvent, and then mixed, and then the solvent is removed.

(4) A method in which the above methods (1) to (3) are combined. As described above, the ethylene / α-olefin copolymer (A) and the ethylene-based copolymer composition (A ′) according to the present invention both have excellent moldability, and have excellent transparency and mechanical strength. Although an excellent film can be produced, it can be used in combination with other polymers, preferably an ethylene / α-olefin copolymer.
As such another ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer (D) described below is particularly preferably used.

The ethylene / α-olefin copolymer (D) used in the present invention comprises ethylene and α-olefin having 3 to 20 carbon atoms.
-A random copolymer with an olefin. As the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

Ethylene / α-olefin copolymer (D)
Then, the structural unit derived from ethylene is 50 to 100
%, Preferably 55-99% by weight, more preferably 6% by weight.
It is present in an amount of from 5 to 98% by weight, most preferably from 70 to 96% by weight, the constituent units derived from C3-20 alpha-olefins being from 0 to 50% by weight, preferably from 1 to 45% by weight, Preferably from 2 to 35% by weight, most preferably 4%
Desirably it is present in an amount of up to 30% by weight.

The ethylene / α-olefin copolymer (D) preferably has the following properties (D-i) and (D-ii). ) ~
It is more preferable to have the characteristics as shown in (D-iv). (D-i) The density (d) is 0.850 to 0.980 g /
cm ³ , preferably 0.910 to 0.960 g / c
m ³ , more preferably 0.915 to 0.955 g / cm
³ , most preferably 0.920 to 0.950 g / cm ³
In the range. (D-ii) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 0.4 to 1.2 dl / g.
It is in the range of 5 dl / g, more preferably 0.5 to 1.23 dl / g. (D-iii) Temperature (Tm) at the maximum peak position in an endothermic curve measured by a differential scanning calorimeter (DSC).
(° C.)) and density (d (g / cm ³ )) It is desirable to satisfy the relationship shown by. (D-
iv) When the fraction (W (% by weight)) and the density (d (g / cm ³ )) of the n-decane-soluble component at room temperature are MFR ≦ 10 g / 10 minutes, W <80 × exp (-100) (d-0.88)) + 0.1 preferably W <60 × exp (-100 (d-0.88)) + 0.1, more preferably W <40 × exp (-100 (d-0.88)) + 0.1 MFR> 10 g / 10 In the case of minutes, the relationship represented by W <80 × (MFR-9) ^0.26 × exp (-100 (d−0.88)) + 0.1 is satisfied.

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

However, the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (D) are not the same, and the ethylene / α-olefin copolymers (B) and (C) And the ethylene / α-olefin copolymer (D) are not the same. Specifically, ethylene / α
The olefin copolymer (D) and the ethylene / α-olefin copolymers (A) to (C) can be distinguished by the following characteristics.

That is, the ethylene / α-olefin copolymer (D) is required to define the copolymer (A) (A-olefin copolymer).
It is a copolymer that does not satisfy at least one of the requirements i) to (A-iii).

The ethylene / α-olefin copolymer (D) is a component (B-iii) which defines the copolymer (B).
It is a copolymer that does not satisfy at least one requirement of (B-vii).

Further, the ethylene / α-olefin copolymer (D) is required to define the copolymer (C) (C-ii).
It is a copolymer that does not satisfy at least one of the requirements (i) to (Cv).

The ethylene / α-olefin copolymer (D) is, for example, an olefin containing (a) an organoaluminum oxy compound and (b-III) a transition metal compound represented by the following general formula (III). It is obtained by copolymerizing ethylene and an olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst. (A) The organic aluminum oxy compound is the same as that described in the method for producing the ethylene / α-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used, or prepolymerization may be performed. The amount of each component used, the pre-polymerization conditions and the main polymerization conditions are also the same
This is the same as in the case of producing the α-olefin copolymer (A).

Hereinafter, the transition metal compound (b-III) will be described. (B-III) Transition metal compound Transition of group 4 of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton used in the production of the ethylene / α-olefin copolymer (D) The metal compound (hereinafter sometimes referred to as “component (b-III)”) is a compound of the periodic table 4 containing a ligand having a cyclopentadienyl skeleton.
The transition metal compound is not particularly limited as long as it is a group 5 transition metal compound, but is preferably a transition metal compound represented by the following general formula (III).

ML ³ _x (III) In the formula, M is a transition metal atom selected from Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.

X is the valence of the transition metal. L ³ is a ligand coordinating to the transition metal atom M, at least one L ³ is a ligand having a cyclopentadienyl skeleton, and the ligand having a cyclopentadienyl skeleton includes: For example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group Alkyl-substituted cycloalkyl such as methylethylcyclopentadienyl, propylcyclopentadienyl, methylpropylcyclopentadienyl, butylcyclopentadienyl, methylbutylcyclopentadienyl, hexylcyclopentadienyl, etc. Pentadienyl group or indenyl group,
Examples thereof include a 4,5,6,7-tetrahydroindenyl group and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among these ligands having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula (III) contains two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons are ethylene, The bond may be formed via an alkylene group such as propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, or a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

In the formula (III), L ³ other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon having 1 to 12 carbon atoms, similar to L ¹ in the formula (I). Group, alkoxy group, aryloxy group, trialkylsilyl group, halogen atom, hydrogen atom, or SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) It is. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

The transition represented by the general formula (III)
The metal compound can be used, for example, when the valence of the transition metal is 4.
In this case, it is more specifically represented by the following general formula (III ′). R^Two _kR^Three _lR^Four _mR^Five _nM ... (III ') (wherein M is the above transition metal atom and R^TwoIs cyclope
A group (ligand) having an antadienyl skeleton;^Three,
R^FourAnd R^FiveHas a cyclopentadienyl skeleton
Group, alkyl group, cycloalkyl group, aryl group, ara
Alkyl, alkoxy, aryloxy, trialkyl
Lucyl group, SO_ThreeR group, halogen atom or hydrogen atom
Where k is an integer of 1 or more, and k + 1 + m + n = 4
It is. ) In the present invention, in the above general formula, R^Three, R^Four
And R^FiveOne of them has a cyclopentadienyl skeleton
Metallocene compounds that are groups (ligands) such as R
^TwoAnd R^ThreeIs a group having a cyclopentadienyl skeleton
(Ligand) metallocene compounds are preferably used.
You. These groups having a cyclopentadienyl skeleton are
Alkylene groups such as ethylene and propylene,
Substituted alkylene groups such as den, diphenylmethylene, etc.
Rylene group or dimethylsilylene, diphenylsilylene
And substituted silylene groups such as methylphenylsilylene group
They may be connected via any. Also, in this case other
A ligand (eg, R^FourAnd R^Five) Is cyclopentadie
A group having a nyl skeleton, an alkyl group, a cycloalkyl group,
Aryl group, aralkyl group, alkoxy group, aryloxy
Si group, trialkylsilyl group, SO _ThreeR, halogen atom
Or a hydrogen atom.

Examples of the transition metal compound represented by the general formula (III) include bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylene Bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) zirconium bis (methanesulfonato), ethylene bis (indenyl) zircon Bis (p-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) ) Zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis ( Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (a Denier) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylene-bis (4,5,6,
7-tetrahydroindenyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium Dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride , Bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride Domonohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclo (Pentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconiumbis (p-toluenesulfonate) , Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zil Dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride , Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium Mudichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride and the like Can be

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted cyclopentadienyl ring includes 1,2,3- and 1,2,4-substituted Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
And isomers.

In the above zirconium compounds, compounds in which zirconium is replaced by titanium or hafnium can also be used. The above general formula (II
The transition metal compound represented by I) includes the aforementioned general formula (I)
And the transition metal compound (b-II) represented by the general formula (II).

Ethylene / α-olefin copolymer (D)
Is a method for copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst so that the density of the obtained copolymer is 0.850 to 0.980 g / cm ^3. It can be manufactured by doing.

Ethylene / α-olefin copolymer (D)
Is the above-mentioned ethylene / α-olefin copolymer (A)
Alternatively, it is preferably used in a proportion of 99 to 60 parts by weight, more preferably 95 to 60 parts by weight, based on 100 parts by weight of the ethylene-based copolymer composition (A ').

Ethylene / α-olefin copolymer (D)
And the above-mentioned ethylene / α-olefin copolymer (A)
Alternatively, the composition with the ethylene-based copolymer composition (A ′) can be produced by using the known method described above. It can also be produced by a multi-stage polymerization method in which copolymerization is divided into two or more stages having different reaction conditions using one or a plurality of polymerization vessels.

Ethylene / α-olefin copolymer (A) and ethylene copolymer composition (A ′) according to the present invention
Is used without particular limitation in the field where ethylene-based copolymers have been conventionally used, but is particularly suitably used for films such as cast films and inflation films and sheets such as extruded sheets. Normal air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-
A film can be obtained by processing by die film molding, water cooling inflation molding, or the like. The film formed in this manner is excellent in transparency and mechanical strength, and has a heat sealing property, which is a characteristic of ordinary LLDPE.
It has hot tack properties, heat resistance, good blocking properties, and the like. Further, since the composition distribution of the ethylene / α-olefin copolymer or the ethylene-based copolymer composition is extremely narrow, there is no stickiness on the film surface. Furthermore, since the melt tension is high, the bubble stability during inflation molding is excellent.

A film obtained by molding the ethylene / α-olefin copolymer (A) and the ethylene-based copolymer composition (A ′) includes a standard bag, a sugar bag, an oil packaging bag, It is suitable for various packaging films such as water packaging bags and agricultural materials. Further, it can be used as a multilayer film by being bonded to a substrate such as nylon or polyester.

The process for producing an ethylene / α-olefin copolymer according to the present invention comprises the steps of (a) the organoaluminum oxy compound, (b-I) transition metal compound, and (b-II) transition metal compound. Is characterized in that ethylene and an α-olefin having 6 to 8 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst.

The carrier (c) and the organoaluminum compound (d) may be used or prepolymerization may be performed in the same manner as described in the method for producing the ethylene / α-olefin copolymer (A). The amounts of the components used, the prepolymerization conditions and the main polymerization conditions are the same as in the case of producing the ethylene / α-olefin copolymer (A).

[0187]

The ethylene / α-olefin copolymer and ethylene copolymer composition of the present invention have high melt tension and excellent moldability. From such an ethylene / α-olefin copolymer and ethylene-based copolymer composition, a film having excellent transparency and mechanical strength can be produced.

[0188]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

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

[Gloss (gloss)] JIS Z874
Measured according to 1. [Dart Impact Strength] ASTM D 1709 A
It was measured according to the method.

[0191]

[Preparation Example 1] [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. Thereafter, 28.7 liters of a toluene solution of methylaluminoxane (Al; 1.33 mol / l) was added dropwise over 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, and then heated to 95 ° C. over 1.5 hours.
The reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. Bis (methylcyclopentadienyl)
13. a toluene solution of zirconium dichloride (Zr;
(0 mmol / liter) was added dropwise at 80 ° C. over 30 minutes, followed by reaction at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst 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 0.85 kg of the solid catalyst obtained above were added.
77 g of 1-hexene was added, and ethylene was prepolymerized at 35 ° C. for 3.5 hours to obtain a prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst.

[Polymerization] Using a continuous fluidized-bed gas-phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. 0.05 mmol of the prepolymerized catalyst prepared above in terms of zirconium atoms
/ H, 10 mmol / h of triisobutylaluminum
And ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.0
20, hydrogen / ethylene = 9.5 × 10 ⁻⁴ , ethylene concentration = 50%). The yield of the polymer was 4.1 kg / h. The obtained ethylene / α-olefin copolymer (B-
1) was melt-kneaded and pelletized. Table 1 shows the melt properties and the like.

[0195]

[Preparation Example 2] [Preparation of catalyst component] In [Preparation of catalyst component] in Preparation Example 1, a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 1
4.0 mmol / l) Instead of 20.0 l, bis (1,3-nbutylmethylcyclopentadienyl)
A toluene solution of zirconium dichloride (Zr; 34.
(0 mmol / liter) A solid catalyst component was prepared in the same manner except that 8.2 liter was used.

[Preparation of Prepolymerized Catalyst] A prepolymerized catalyst was obtained in the same manner as in Preparation Example 1, except that the solid catalyst component obtained in [Preparation of Catalyst Component] was used.

[Polymerization] Using the prepolymerized catalyst obtained in the above [Preparation of Prepolymerized Catalyst], the gas composition was 1-hexene / ethylene = 0.020, hydrogen / ethylene = 5.0 × 1.
An ethylene copolymer (C-1) was obtained in the same manner as in Preparation Example 1 except that 0 ^-4 and ethylene concentration = 50%.
Table 1 shows the properties of the obtained ethylene copolymer (C-1).

[0198]

[Example 1] [Preparation of catalyst component] In [Preparation of catalyst component] of Preparation Example 1, a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 1
4.0 mmol / l) Instead of 20.0 l, bis (1,3-n-butylmethylcyclopentadienyl)
A toluene solution of zirconium dichloride (Zr; 34.
5.8 liter and a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter)
A solid catalyst component was prepared in the same manner except that 6.0 liter was used.

[Preparation of Preliminary Polymerization Catalyst] A prepolymerization catalyst was obtained in the same manner as in Preparation Example 1, except that the solid catalyst component obtained in the above [Preparation of Catalyst Component] was used.

[Polymerization] Using the prepolymerized catalyst obtained in the above [Preparation of Prepolymerized Catalyst], the gas composition was 1-hexene / ethylene = 0.020, hydrogen / ethylene = 4.5 × 1.
An ethylene copolymer (A-1) was obtained in the same manner as in Preparation Example 1, except that 0 ^-4 and ethylene concentration = 50%.
The properties of the obtained ethylene copolymer (A-1) are shown in Table 1.

[0201]

Example 2 [Polymerization] Ethylene was prepared in the same manner as in Example 1 except that the gas composition was adjusted so that the MFR and density became the ethylene / α-olefin copolymer (A-2) shown in Table 1. -The alpha-olefin copolymer (A-2) was obtained.

[0202]

Example 3 [Polymerization] Ethylene was prepared in the same manner as in Example 1 except that the gas composition was adjusted so that the MFR and density became the ethylene / α-olefin copolymer (A-3) shown in Table 1. -The alpha-olefin copolymer (A-3) was obtained.

[0203]

Comparative Example 1 [Polymerization] An ethylene was prepared in the same manner as in Preparation Example 2 except that the gas composition was adjusted so that the MFR and density became the ethylene / α-olefin copolymer (C-2) shown in Table 1. -The alpha-olefin copolymer (C-2) was obtained.

[0204]

Comparative Example 2 [Preparation of Catalyst Component] In [Preparation of Catalyst Component] of Preparation Example 1, a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 1
(4.0 mmol / l) Instead of 20.0 l, a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr; 28.0 mm) was used.
ol / liter) A solid catalyst component was prepared in the same manner except that 10.0 liter was used.

[Preparation of Preliminary Polymerization Catalyst] A prepolymerization catalyst was obtained in the same manner as in Preparation Example 1, except that the solid catalyst component obtained in the above [Preparation of Catalyst Component] was used.

[Polymerization] Using the prepolymerized catalyst obtained in the above [Preparation of Prepolymerized Catalyst], the gas composition was adjusted so that the MFR and the density became the ethylene / α-olefin copolymer (D) shown in Table 1. Was prepared in the same manner as in Preparation Example 1, except that was prepared, to obtain an ethylene / α-olefin copolymer (D).

[0207]

Example 4 The ethylene / α-olefin copolymers (B-1) and (C-1) obtained in Preparation Example 1 and Preparation Example 2 were converted to (B-1) / (C-1) = 80 / The mixture was pelletized by melt-kneading at a weight ratio of 20 to obtain an ethylene-based copolymer composition (A'-1). The obtained copolymer composition (A'-
Table 1 shows the melt properties and the like of 1).

[0208]

Examples 5 to 8 and

Comparative Examples 3 and 4 [Film Forming] Inflation films were obtained from the pellets of the ethylene / α-olefin copolymer or ethylene copolymer composition shown in Table 3 under the following conditions. 20mmφ · L / D = 26
25mmφ die, lip width 0.7 using a single screw extruder
mm, using a single slit air ring, air flow rate = 90 liter / min, extrusion rate = 9 g / min, blow ratio = 1.8, take-up speed = 2.4 m / min, processing temperature = 200 ° C., thickness = 30 μm. Was obtained by inflation molding. Table 3 shows the physical properties of the film.

[0209]

Example 9 Same as Example 1 except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymers (A-4) and (A-5) shown in Table 1. And the ethylene / α-olefin copolymer (A-
4) and (A-5) were produced. The weight ratio of the ethylene / α-olefin copolymer (A-4) and (A-5) was (A-
4) / (A-5) = 60/40, melt-kneaded and pelletized to obtain an ethylene copolymer composition (L-1). Using the pellets of the ethylene copolymer composition (L-1), an inflation film was obtained in the same manner as in Examples 5 to 8. The results are shown in Tables 2 and 3.

[0210]

Example 10 An ethylene / α-olefin was prepared in the same manner as in Example 1 except that the gas composition was adjusted so that the density and the MFR became the ethylene / α-olefin copolymer (A-6) shown in Table 1. An olefin copolymer (A-6) was produced. This ethylene / α-olefin copolymer (A-6)
And the ethylene / α-olefin copolymer (A-5) produced in Example 9 by weight ratio (A-6) / (A-5) = 60 /
The mixture was melt-kneaded at 40 and pelletized to obtain an ethylene copolymer composition (L-2). Using the pellets of the ethylene copolymer composition (L-2), a blown film was obtained in the same manner as in Examples 5 to 8. Tables 2 and 3 show the results.
Shown in

[0211]

EXAMPLE 11 Ethylene / α-olefin copolymers (A-7) and (A-8) whose density and MFR are listed in Table 1
In the same manner as in Example 1 except that the gas composition was adjusted so as to obtain an ethylene / α-olefin copolymer (A-
7) and (A-8) were produced. The weight ratio of the ethylene / α-olefin copolymer (A-7) and (A-8) was (A-
7) / (A-8) = 60/40, melt-kneaded and pelletized to obtain an ethylene copolymer composition (L-3). Using the pellets of the ethylene copolymer composition (L-3), an inflation film was obtained in the same manner as in Examples 5 to 8. The results are shown in Tables 2 and 3.

[0212]

[Table 1]

[0213]

[Table 2]

[0214]

[Table 3]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst used in the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takeshi Yoshitsuji 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc.

Claims (10)

[Claims] 1. A copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms, wherein (A-i) a melt tension (MT) at 190 ° C. and a melt flow rate (MFR) are: 0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84 is satisfied, and (A-ii) the activation energy of the flow obtained from the shift factor of time-temperature superposition of the flow curve ((E _a ) × 10 ⁻⁴ J / molK), the number of carbon atoms (C) of the α-olefin in the copolymer, and the content (x mol%) of the α-olefin in the copolymer are represented by (0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039L
n (C-2) +0.1660) × x + 2.87 is satisfied, and (A-iii) the copolymer is subjected to inflation molding to produce a film having a thickness of 30 μm. Haze) satisfying the following relationship: ethylene / α-olefin copolymer (A); shear stress at 190 ° C. is 2.4 × 1
0 ⁶ dyne / cm flowability index is defined as a shear rate when reaching the ² (FI) and melt flow rate (M
FR) When FI ≧ 100 × MFR When α-olefin has 6 carbon atoms (C), Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) The shear stress at 190 ° C. is 2 .4 × 10 ⁶ dyne / cm
When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when reaching ² are FI <100 × MFR When the number of carbon atoms (C) of the α-olefin is 6, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^{0.1 When the} number of carbon atoms (C) of the α-olefin is 7 or 8, Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) (where d is the density ( g / cm ³ ), and MT indicates the melt tension (g).) (A) an organoaluminum oxy compound,
(B-I) a transition metal compound represented by the following general formula (I)
At least one transition metal compound selected from the group consisting of:¹ _X ... (I) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L¹Is a ligand that coordinates to the transition metal atom M,
At least two of these ligands L¹Is 3 carbon atoms
At least one group selected from hydrocarbon groups of 10 to 10
A substituted cyclopentadienyl group having
Ligands other than pentadienyl groups L¹Has 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, tria
A rusilsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal M. ) (B-II) The following general
At least one selected from transition metal compounds represented by formula (II)
And one transition metal compound, ML^Two _X ... (II) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L^TwoIs a ligand that coordinates to the transition metal atom M,
At least two of these ligands L^TwoIs methyl
Clopentadienyl group or ethylcyclopentadienyl
A methylcyclopentadienyl group or an ethyl group.
Ligands other than rucyclopentadienyl group L ^TwoIs the carbon number
1 to 12 hydrocarbon groups, alkoxy groups, aryloxy
Group, trialkylsilyl group, halogen atom or hydrogen atom
And X is the valence of the transition metal atom M. From)
Ethylene and carbon in the presence of an olefin polymerization catalyst
Claims obtained by copolymerizing an α-olefin of Formulas 6 to 8
Item 7. The ethylene / α-olefin copolymer according to Item 1.
(A). 3. An olefin polymerization catalyst comprising (a) an organoaluminum oxy compound, (b-I) a transition metal compound and (b-II) a transition metal compound supported on a carrier. The ethylene / α-olefin copolymer (A) according to claim 2, which is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms. 4. A copolymer of (B) ethylene and an α-olefin having 6 to 8 carbon atoms, wherein the (Bi) density is 0.8%.
(B-ii) in the range of 80 to 0.970 g / cm ^3.
The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.02 to 200 g / 10 minutes, and (B-iii) the decane-soluble component content ratio (W) and the density (d) at room temperature. When MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp (− 100 (d-0.88)) + 0.1, the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by the differential scanning calorimeter (DSC) are satisfied. Tm <400 × d−248 is satisfied, and (B−v) the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) are 9.0 × MFR ^−0.65 >MT> 2.2. × satisfy the relationship represented by MFR ^-0.84, (B-vi) the flow curve of time - determined from temperature superposition of shift factor Flow activation energy ^{_{((E a) × 10 -4}} J / molK), the carbon number of the alpha-olefin in the copolymer (C), alpha-olefin content of the copolymer (x mol %) Is (0.039Ln
(C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +
0.1660) × x + 2.87 is satisfied, and (B−vi
i) ethylene · α wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is represented by 2.2 <Mw / Mn <3.5. An olefin copolymer, (C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms, wherein the (Ci) density is 0.8
(C-ii) in the range of 80 to 0.970 g / cm ^3.
The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.02 to 200 g / 10 minutes, and (C-iii) the decane-soluble component content rate (W) at room temperature and the density (d). When MFR ≦ 10 g / 10 min, W <80 × exp (-100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp ( -100 (d-0.88)) + 0.1, (C-iv) temperature (Tm) and density (d) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC). ^{Satisfies the} relationship expressed by Tm <400 × d-248, and (C−v) the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) are expressed by MT ≦ 2.2 × MFR− ^0.84 . And an ethylene-α-olefin copolymer to be obtained. Ethylene copolymer having a ratio of melt (MFR (C)) to melt flow rate (MFR (B)) of (B): 1 <(MFR (C)) / (MFR (B)) ≦ 20 Composition (A '). 5. The ethylene / α-olefin copolymers (B) and (C) are both ethylene / hexene-1 copolymers, and (A′-i) the melt tension (MT) at 190 ° C. and the melt The flow rate (MFR) satisfies the relationship of 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84 , and (A′-ii) the shift factor of the time-temperature superposition of the flow curve The obtained flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) and the carbon number (C) of hexene-1 in the copolymers (B) and (C)
And the total content (x mol%) of hexene-1 in the copolymers (B) and (C) is (0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≤ (0.039L
n (C-2) +0.1660) × x + 2.87 (A′-iii) When the copolymer composition is blown-molded to produce a 30 μm thick film, 5. The ethylene copolymer composition (A ′) according to claim 4, wherein the haze of the ethylene-based copolymer composition satisfies the following relationship: a shear stress at 190 ° C. of 2.4 × 10 ⁶ dyne / cm ^2. When the fluidity index (FI) defined by the shear rate at the time of reaching and the melt flow rate (MFR) is FI ≧ 100 × MFR, Haze <0.45 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 Shear stress at 190 ° C. is 2.4 ×
When the fluidity index (FI) defined by the shear rate when reaching 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR, Haze <0.25 / (1-d) × log (3 × MT ^1.4 )
× (C-3) ^0.1 (where d is density (g / cm ³ ), MT is melt tension (g), and C is the number of carbon atoms of hexene-1, that is, “6”). 6. In addition to the requirements of (A′-i) to (A′-iii), (A′-iv) the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC Ratio (Mw
The ethylene copolymer composition (A ′) according to claim 5, wherein (Mn) satisfies 2.0 ≦ Mw / Mn ≦ 2.5. 7. (A) The ethylene / α-olefin copolymer according to any one of claims 1 to 3, (D) (a) an organoaluminum oxy compound, and (b-III) cyclopentadienyl Ethylene and α-C 3-20 in the presence of a catalyst for olefin polymerization containing a transition metal compound belonging to Group 4 of the periodic table containing a ligand having a skeleton.
(D-i) having a density in the range of 0.850 to 0.980 g / cm ³ , and (D-ii) an intrinsic viscosity [η measured at 135 ° C. in decalin. Is in the range of 0.4 to 8 dl / g.
An ethylene copolymer composition comprising an olefin copolymer (however, the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (D) are not the same). Stuff. 8. (A ′) The ethylene copolymer composition according to any one of claims 4 to 6, (D) (a) an organoaluminum oxy compound, and (b-III) cyclopentadienyl Ethylene and α-C 3-20 in the presence of a catalyst for olefin polymerization containing a transition metal compound belonging to Group 4 of the periodic table containing a ligand having a skeleton.
(D-i) having a density in the range of 0.850 to 0.980 g / cm ³ , and (D-ii) an intrinsic viscosity [η measured at 135 ° C. in decalin. Is in the range of 0.4 to 8 dl / g.
An ethylene-based copolymer comprising an olefin copolymer (provided that the ethylene / α-olefin copolymers (B) and (C) and the ethylene / α-olefin copolymer (D) are not the same) Copolymer composition. 9. An organic aluminum oxy compound (a),
(B-I) a transition metal compound represented by the following general formula (I)
At least one transition metal compound selected from the group consisting of:¹ _X ... (I) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L¹Is a ligand that coordinates to the transition metal atom M,
At least two of these ligands L¹Is 3 carbon atoms
At least one group selected from hydrocarbon groups of 10 to 10
A substituted cyclopentadienyl group having
Ligands other than pentadienyl groups L¹Has 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, tria
A rusilsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal M. ) (B-II) The following general
At least one selected from transition metal compounds represented by formula (II)
And one transition metal compound, ML^Two _X ... (II) (wherein M is a transition metal atom selected from Group 4 of the periodic table)
Yes, L^TwoIs a ligand that coordinates to the transition metal atom M,
At least two of these ligands L^TwoIs methyl
Clopentadienyl group or ethylcyclopentadienyl
A methylcyclopentadienyl group or an ethyl group.
Ligands other than rucyclopentadienyl group L ^TwoIs the carbon number
1 to 12 hydrocarbon groups, alkoxy groups, aryloxy
Group, trialkylsilyl group, halogen atom or hydrogen atom
And X is the valence of the transition metal atom M. From)
Ethylene and carbon in the presence of an olefin polymerization catalyst
Characterized in that it is copolymerized with an α-olefin of Formulas 6 to 8.
For producing an ethylene / α-olefin copolymer. 10. An olefin polymerization catalyst comprising (a) an organoaluminum oxy compound, (b-I) a transition metal compound and (b-II) a transition metal compound supported on a carrier. 10. The method for producing an ethylene / α-olefin copolymer according to claim 9, wherein ethylene and an α-olefin having 6 to 8 carbon atoms are copolymerized.