JP2006161059A - Ethylene-alpha olefin copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylenic copolymer composition having excellent transparency, mechanical strengths and moldability. <P>SOLUTION: The ethylene-α-olefin copolymer relating to this invention is a copolymer from ethylene and an α-olefin of 6 to 8 carbon atoms, in which the melt tension (MT) and the melt flow rate (MFR) satisfy the following relation: 9.0 × MFR<SP>-0.65</SP>> MT > 2.2 × MFR<SP>-0.84</SP>; fluidity activation energy ((Ea) × 10<SP>-4</SP>J/mol K), the carbon number (C) of the α-olefin in the copolymer and the content of the α-olefin in the copolymer (x mol%) are related to satisfy (0.039Ln(C-2) + 0.0096)×x +2.87 < Ea × 10<SP>-4</SP>≤ (0.039Ln(C-2) + 0.1660)×x +2.87; in addition, when film is inflated, the Haze of the film satisfies specific relations. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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. The present invention also relates to an ethylene copolymer composition having substantially the same composition and utility as the ethylene / α-olefin copolymer.

Furthermore, the present invention relates to a composition of the above ethylene / α-olefin copolymer or ethylene copolymer composition and another ethylene copolymer.
Furthermore, the present invention relates to a method for producing the ethylene / α-olefin copolymer as described above.

  Ethylene copolymers are molded by various molding methods and are used for various purposes. The ethylene-based copolymer has different required characteristics depending on the molding method and application. For example, when an inflation film is to be molded at a high speed, there is no bubble swaying or tearing, and in order to stably perform high speed molding, the ethylene-based copolymer has a melt tension (melting tension) for its molecular weight. You must choose the bigger one. Similar properties are necessary to prevent sagging or tearing in hollow molding or to minimize width drop in T-die molding.

  By the way, a method for improving moldability by improving the melt tension (melting tension) or expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in JP-A-56-56. No. 90810 or JP-A-60-106806 has been proposed. However, ethylene polymers generally obtained using a titanium-based catalyst, especially low density ethylene copolymers, have a wide composition distribution and may contain components that cause stickiness when formed into a molded body such as a film. It has been desired to further reduce the components that cause many stickiness.

  Among ethylene polymers produced using Ziegler-type catalysts, ethylene polymers obtained using chromium-based catalysts have a relatively high melt tension, but further thermal stability has been desired. .

  Many ethylene-based copolymers obtained using an olefin polymerization catalyst containing a transition metal metallocene compound have high melt tension and good thermal stability, and are expected to meet the above-mentioned demand. However, in an ethylene-based copolymer obtained with a metallocene catalyst, generally, melt tension (MT) and flow activation energy (Ea) are in a proportional relationship.

  As described above, a polymer having a large melt tension is excellent in bubble stability and thus has good moldability. However, the flow activation energy (Ea) is high, which means that the temperature dependence 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 lowered.

  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 is poor.

  The present invention has been made in view of the situation as described above, and can produce a film excellent in transparency and mechanical strength, and has excellent moldability and an ethylene / α-olefin copolymer, and the same. An object of the present invention is to provide an ethylene copolymer composition having substantially the same composition and usefulness.

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,
(Ai) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) determined from the shift factor of time-temperature superposition of the flow curve, and the number of carbon atoms of the α-olefin in the copolymer (C)
And the α-olefin content (x mol%) in the copolymer
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A-iii) When the copolymer is blown to produce a film having a thickness of 30 μm, the haze of the film satisfies the following relationship.

When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI ≧ 100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
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 )
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR α -When the number of carbon atoms (C) of the 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 is the melt tension (g)).

The method for producing the ethylene / α-olefin copolymer (A) according to the present invention comprises:
(A) an organoaluminum oxy compound;
(B-I) at least one transition metal compound selected from transition metal compounds represented by the following general formula (I);
ML ¹ _X (I)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand coordinated to transition metal atom M, and at least two of these ligands L ¹ are A substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups having 3 to 10 carbon atoms, and the ligand L ¹ other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is a valence of the transition metal M.) (b-II) represented by the following general formula (II) At least one transition metal compound selected from transition metal compounds;
ML ² _X (II)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are A methylcyclopentadienyl group or an ethylcyclopentadienyl group, and the ligand L ² other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy A group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M.)
It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms in the presence of an olefin polymerization catalyst.

In the above catalyst, the (a) organoaluminum oxy compound, (b-I) transition metal compound and (b-II) transition metal compound are:
(C) It is preferably supported on a carrier.

The ethylene / α-olefin copolymer (A) as described above is excellent in moldability, and can produce a film excellent in transparency and mechanical strength.
The ethylene-based copolymer composition (A ′) according to the present invention has substantially the same composition and utility as the ethylene / α-olefin copolymer,
(B) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Bi) The density is in the range of 0.880 to 0.970 g / cm ³ ,
(B-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(B-iii) Decane-soluble component amount ratio (W) and density (d) at room temperature,
When MFR ≦ 10g / 10min,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(B-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured with a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(Bv) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(B-vi) Flow activation energy ((E _a ) × 10 ⁻⁴ J / mol K) determined from the shift factor of time-temperature superposition of the flow curve, and the number of carbon atoms of the α-olefin in the copolymer (C)
And the α-olefin content (x mol%) in the copolymer
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(B-vii) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by GPC (Mw
/ Mn)
2.2 <Mw / Mn <3.5
An ethylene / α-olefin copolymer characterized by the following:
(C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Ci) the density is in the range of 0.880-0.970 g / cm ³ ,
(C-ii) The melt flow rate (MFR) at 190 ° C. and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(C-iii) Decane-soluble component amount ratio (W) at room temperature and density (d) are MFR ≦ 10
When g / 10 minutes
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(C-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
( ^Cv ) The melt tension (MT) at 190 ° C. and the melt flow rate (MFR) are MT ≦ 2.2 × MFR ^−0.84
An ethylene / α-olefin copolymer represented by:
An ethylene copolymer composition (A ′) comprising:
The ratio of the melt flow rate (MFR (C)) of (C) to the melt flow rate (MFR (B)) of (B) is 1 <(MFR (C)) / (MFR (B)) ≦ 20
It is characterized by being.

In the ethylene copolymer composition (A ′) of the present invention, both the ethylene / α-olefin copolymers (B) and (C) are ethylene / hexene-1 copolymers,
(A′-i) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A′-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / mol K) determined from the time-temperature superposition shift factor of the flow curve, and the copolymers (B) and (C) The relationship between the carbon number (C) of hexene-1 in the polymer 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 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A′-iii) When the copolymer composition is subjected to inflation molding to produce a film having a thickness of 30 μm, the haze of the film preferably satisfies the following relationship.

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

Furthermore, the ethylene-based copolymer composition (A ′) of the present invention has a weight average determined by (A′-iv) GPC in addition to the requirements (A′-i) to (A′-iii). Ratio of molecular weight (Mw) to number average molecular weight (Mn) (Mw
/ Mn)
2.0 ≦ Mw / Mn ≦ 2.5
It is preferable to satisfy.

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) ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton. Obtained by copolymerization,
(Di) The density is in the range of 0.850 to 0.980 g / cm ³ ,
(D-ii) An ethylene / α-olefin copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g can be blended.

  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. It is not the same as the α-olefin copolymer (D).

The method for producing an ethylene / α-olefin copolymer according to the present invention comprises:
(A) an organoaluminum oxy compound, (b-I) a transition metal compound, and (b-II)
In the presence of an olefin polymerization catalyst comprising a transition metal compound, ethylene and an α-olefin having 6 to 8 carbon atoms are copolymerized.

  The ethylene / α-olefin copolymer and the ethylene copolymer composition of the present invention have high melt tension and excellent moldability. A film excellent in transparency and mechanical strength can be produced from such an ethylene / α-olefin copolymer and an ethylene copolymer composition.

Hereinafter, the ethylene / α-olefin copolymer (A), the production method thereof, and the ethylene copolymer composition (A ′) according to the present invention 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” includes not only homopolymers but also copolymers. May be used with the intention.
Ethylene / α-olefin copolymer (A)
The 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. The α-olefin having 6 to 8 carbon atoms used for copolymerization with ethylene is preferably a linear α-olefin having no branch, and specifically, for example, 1-hexene, 1-heptene, 1-octene. In particular, hexene-1 is preferably used.
The ethylene / α-olefin copolymer (A) according to the present invention includes the following (Ai) to (A-iii):
).
( ^Ai ) 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 relationship indicated by is satisfied.
The ethylene / α-olefin copolymer having such characteristics has a high melt tension (MT), and therefore has good moldability.
The MFR is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-65T.

The melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is, the produced polymer powder is melted by a conventional method and pelletized to obtain a measurement sample. Using an MT measuring instrument manufactured by Toyo Seiki Seisakusho, the resin temperature is 190 ° C., the extrusion speed is 15 mm / min, and the winding speed is 10 to 20 m / min. The nozzle diameter was 2.09 mmφ and the nozzle length was 8 mm. At the time of pelletization, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant is added to the ethylene / α-olefin copolymer in advance as a heat stabilizer. 0.1% by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were blended.
(A-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) determined from the time-temperature superposition shift factor of the flow curve and the carbon number of the α-olefin in the copolymer (C
) And the α-olefin content (x mol%) in the copolymer,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1500) × x + 2.87
More preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1300) × x + 2.87
The relationship indicated by is satisfied.

In order to improve the film moldability, it is necessary to improve the melt tension, and it is known that introduction of long chain branching is effective for that purpose. E _a of an ethylene / α-olefin copolymer having no long chain branch is represented by E _a × 10 ⁻⁴ = (0.039 Ln (C-2) +0.0096) × x + 2.87. If a long chain branch is present, E _a becomes large. Therefore, if E _a × 10 ⁻⁴ > (0.039Ln (C-2) +0.0096) × x + 2.87, it is estimated that a long chain branch exists, Film formability and transparency are improved. On the other hand, when E _a × 10 ⁻⁴ > (0.039Ln (C-2) +0.1660) × x + 2.87, although the moldability is excellent, film strength and film transparency are deteriorated, which is not preferable.

The measurement of the flow activation energy (E _a ) can be performed by, for example, “Polymer Experiments Vol. 9 Thermodynamic Properties I (Polymer Society, Polymer Experiments Editorial Committee, Kyoritsu Shuppan Co., Ltd. ) ”, The viscoelastic frequency dependence is measured, and the activation energy (E _a ) of the flow is obtained from the shift factor of the time-temperature superposition. When the graph of 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 (thermorheological simplicity). The amount Log (aT) by which the data at each measurement temperature is shifted so that it can be overlaid with the reference temperature data is plotted on the slope of the straight line obtained by plotting against the inverse 1 / T of the measurement temperature (absolute temperature) 2.303 Multiplying by R (R is a gas constant), the activation energy is obtained as a constant independent of temperature.

Specifically, _Ea is measured as follows.
Using a rheometer RDS-II manufactured by Rheometrics, the angular velocity (ω (rad / sec)) dispersion of the storage elastic modulus (G ′ (dyne / cm ² )) was measured. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2 mm. The measurement temperatures were 130, 170, 200, and 230 ° C., and G ′ was measured in the range of 0.04 ≦ ω ≦ 400 at each temperature. In the case of measuring at 130 ° C., in order to completely melt the crystal, the temperature was raised to 150 ° C. and then set to 130 ° C., and then measured. The amount of strain was appropriately selected in the range of 2 to 25% so that the torque in the measurement range could be detected and the torque was not exceeded. After the measurement, flow curves under four temperature conditions were superimposed with 130 ° C. as the reference temperature, and E _a was obtained from the Arrhenius type plot of the shift factor. The calculation was performed using analysis software RHIOS attached to RDS-II.
(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.

When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI ≧ 100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
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 )
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR α -When the number of carbon atoms (C) of the 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 is the melt tension (g)).

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

In addition, it changes by changing the diameter of a nozzle as follows by MFR (g / 10min) of resin to measure.
0.5 mm when MFR> 20
1.0 mm when 20 ≧ MFR> 3
2.0 mm when 3 ≧ MFR> 0.8
3.0mm when 0.8 ≧ MFR
The density (d) is determined by measuring the melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg, heat-treating the strand at 120 ° C. for 1 hour, gradually cooling to room temperature over 1 hour, and then the density gradient tube Measure with

In addition to the above requirements, the ethylene / α-olefin copolymer (A) according to the present invention preferably satisfies the following requirements.
In the ethylene / α-olefin copolymer (A) according to the present invention, 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, and most preferably. Is present in an amount of 70 to 96% by weight, and the 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, Particularly preferably, it is present in an amount of 4 to 30% by weight.
The composition of the ethylene / α-olefin copolymer is usually a ¹³ C-NMR spectrum of a sample in which about 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. Measurement frequency 25.05MHz, spectrum width 1500Hz
, Measured under measurement conditions of a pulse repetition time of 4.2 sec. And a pulse width of 6 μsec.
The density (d) of the ethylene / α-olefin copolymer (A) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0. .935 g / cm ³ , most preferably in the range of 0.905 to 0.930 g / cm ³ .

The melt flow rate (MFR) of the ethylene / α-olefin copolymer (A) is 0.02 to 200 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10. It is desirable to be in the range of minutes.
The amount of the n-decane soluble component [W (wt%)] and the density [d (g / cm ³ )] at 23 ° C. of the ethylene / α-olefin copolymer (A) is MFR ≦ 10 g / 10 min. When,
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
It is desirable to satisfy the relationship indicated by.

The measurement of the amount of n-decane soluble component of the ethylene / α-olefin copolymer (the smaller the soluble component amount, the narrower the composition distribution) was made by adding about 3 g of the copolymer to 450 ml of n-decane at 145 ° C. After dissolution, the solution is cooled to 23 ° C., the n-decane insoluble part is removed by filtration, and the n-decane soluble part is recovered from the filtrate.
The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the endothermic curve of the ethylene / α-olefin copolymer (A) measured by a differential scanning calorimeter (DSC)
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
It is desirable to satisfy the relationship indicated by.

  The temperature (Tm) at the maximum peak position of the endothermic curve measured with a differential scanning calorimeter (DSC) is about 5 mg of a sample packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, and then at 200 ° C. for 5 minutes. It is calculated | required from the endothermic curve at the time of temperature-falling to room temperature at 20 degrees C / min after hold | maintaining, and then heating up at 10 degrees C / min. The measurement uses a DSC-7 type apparatus manufactured by PerkinElmer.

  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), the n-decane soluble component amount fraction (W) and the density (d) It can be said that an ethylene / α-olefin copolymer having a relationship as described above has a narrow composition distribution.

In the present invention, the ethylene / α-olefin copolymer (A) as described above may be used in combination of two or more.
The ethylene / α-olefin copolymer (A) according to the present invention is:
(A) an organoaluminum oxy compound;
(B-I) at least one transition metal compound selected from the transition metal compounds represented by the general formula (I);
(B-II) ethylene and carbon number in the presence of an olefin polymerization catalyst (Cat-1) formed from at least one transition metal compound selected from the transition metal compounds represented by the general formula (II) It is obtained by copolymerizing with 6-8 α-olefins.

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

First, the respective catalyst components forming the olefin polymerization catalysts (Cat-1) and (Cat-2) will be described.
(A) Organoaluminum oxy compound The organoaluminum oxy compound (a) used in the present invention (hereinafter sometimes referred to as "component (a)") is a conventionally known benzene-soluble aluminoxane. Alternatively, it may be a benzene-insoluble organoaluminum 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 adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the above hydrocarbon medium.

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

(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
In addition, this aluminoxane may contain a small amount of organometallic components. Further, after removing the solvent or the unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, it may be redissolved in the solvent.
Specific examples of organoaluminum compounds used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert- Butyl aluminum, tripentyl aluminum,
Trialkylaluminum such as trihexylaluminum, trioctylaluminum and tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; dialkyl such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride Aluminum halides; Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; Dialkylaluminum aryloxides such as diethylaluminum phenoxide It is.

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 positive numbers and z ≧ 2x)
Isoprenylaluminum represented by the formula can also be used.

The organoaluminum compounds as described above are used alone or in combination. Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons ( Examples thereof include hydrocarbon solvents such as chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used.

Of these solvents, aromatic hydrocarbons are particularly preferred.
The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligrams of Al in 100 ml of benzene, mixing at 60 ° C. for 6 hours with stirring, and then attaching a jacket. Using a G-5 glass filter, hot filtration was performed at 60 ° C., and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the Al atoms present in the total filtrate were removed. It is determined by measuring the abundance (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). The transition metal compound (b-II) is a transition metal compound represented by the following general formula (II).

ML ¹ _X (I)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ¹ are , A substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups having 3 to 10 carbon atoms, and the ligand L ¹ other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is a valence of the transition metal atom M.)
ML ² _X (II)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are A methylcyclopentadienyl group or an ethylcyclopentadienyl group, and the ligand L ² other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy A group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M.)
Hereinafter, the transition metal compound represented by the general formula (I) or (II) will be described more specifically.

In the above general formula (I), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
L ¹ is a ligand coordinated to the transition metal atom M, and at least two of the ligands L ¹ are at least one substituent selected from hydrocarbon groups having 3 to 10 carbon atoms. A substituted cyclopentadienyl group having 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 are methyl group, ethyl group Or it is a C3-C10 hydrocarbon group.

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

Of these, an alkyl group is preferable, and an n-propyl group and an n-butyl group are particularly preferable. In the present invention, the substituted cyclopentadienyl group coordinated to the transition metal is preferably a disubstituted cyclopentadienyl group, 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, or a trialkyl. A silyl 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. More specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are exemplified. 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 and other cycloalkyl groups Examples thereof include aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. be able to.
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-hexylcyclopenta). Dienyl) 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-butylcyclopentadi) Enyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, bis (n-butylcyclopentadienyl) zirconium butoxychloride, 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) Benzalkonium dibenzyl, bis (n- butylcyclopentadienyl) zirconium phenyl chloride, and bis (n- butylcyclopentadienyl) zirconium hydride chloride.

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

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

In the above general formula (II), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are a methylcyclopentadienyl group or an ethylcyclopentadienyl group, and each is the same. It may or may not be.

In the general formula (II), a ligand L ² other than a methylcyclopentadienyl group or an ethylcyclopentadienyl group coordinated to the transition metal atom M is L ¹ in the general formula (I). It is the same C1-C12 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, halogen atom or hydrogen atom.

  Examples of the transition metal compound represented by the general formula (II) include bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis (methylcyclopentadienyl) zirconium dibromide. Bis (ethylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium methoxychloride, bis (ethylcyclopentadienyl) zirconium methoxychloride, bis (methylcyclopentadienyl) zirconium ethoxychloride, bis (Ethylcyclopentadienyl) zirconium ethoxy chloride, bis (methylcyclopentadienyl) zirconium diethoxide, bis (ethylcyclopentadienyl) zirconium diethoxide, (Methylcyclopentadienyl) zirconium methyl chloride, bis (ethylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclo Pentadienyl) zirconium benzyl chloride, bis (ethylcyclopentadienyl) zirconium benzyl chloride, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (ethylcyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadi) Enyl) zirconium phenyl chloride, bis (ethylcyclopentadienyl) zirconium phenyl chloride, bis (methylcyclopentadienyl) zirconium hydride Examples include 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 above-described zirconium compound can be used.
Of these transition metal compounds represented by the general formula (II), bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride are particularly preferable.

In the present invention, at least one transition metal compound selected from the transition metal compounds represented by the above general formula (I) as the transition metal compound and at least selected from the transition metal compounds represented by the above general formula (II) are used. One transition metal compound is used in combination. As a combination method, under the same polymerization conditions, an MFR (MFR (I)) of an olefin polymer obtained from a catalyst component containing only the transition metal compound represented by the general formula (I) as a transition metal compound component, and The ratio 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 to the MFR (MFR (II)) is MFR (I) / MFR (II ) ≦ 20 is preferable.

  Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propylmethylcyclopentadiene) A combination of enyl) zirconium dichloride and 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 (bI) selected from transition metal compounds represented by the above general formula (I) and at least one selected from transition metal compounds represented by the above general formula (II)
The transition metal compound (b-II) is a molar ratio (bI / b-II) of 99/1 to 40/60, preferably 95/5 to 45/55, more preferably 90/10 to 50 /. It is desirable that the amount used is 50, most preferably 85/15 to 55/45.

Hereinafter, at least one selected from the transition metal compound (bI) represented by the general formula (I) and at least one selected from the transition metal compound (b-II) represented by the general formula (II): The transition metal compound catalyst component containing may be described as “component (b)”.
The catalyst for olefin polymerization (Cat-1) used in the present invention is the above organoaluminum oxy compound.
(A), a transition metal compound (b-I) and a transition metal compound (b-II), and the above-described organoaluminum oxy compound (a), transition metal The compound (b-I) and the transition metal compound (b-II) can be supported and used as the catalyst (Cat-2).

(C) Carrier The carrier (c) used as necessary in the present invention is an inorganic or organic compound and has a granular or fine particle shape with a particle size of 10 to 300 µm, preferably 20 to 200 µm. Solids are used. Of these, porous oxides are preferred as the inorganic compounds. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc. Examples of the mixture containing SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. be able to.

Of these, those containing as a main component at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferred.
The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na _2.
SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O
, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such a carrier (c) has different properties depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, The volume is desirably 0.3 to 2.5 cm ³ / g. The carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

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 group is 1.0% by weight or more, preferably 1.5 to 4%. It is desirable that the amount be 0.0% by weight, particularly preferably 2.0 to 3.5% by weight.

Here, the amount of adsorbed water (wt%) and the amount of surface hydroxyl groups (wt%) of the carrier (c) are determined as follows.
[Amount of adsorbed water]
The amount of adsorbed water is the percentage of the weight loss when dried at 200 ° C. under normal pressure and nitrogen flow for 4 hours with respect to the weight before drying.

[Surface hydroxyl group content]
The weight of the support obtained by drying for 4 hours at 200 ° C. under normal pressure and nitrogen flow is X (g), and the surface hydroxyl group obtained by calcining the support for 20 hours at 1000 ° C. disappears. The weight of the fired product is Y (g) and is calculated according to the following formula.
Surface hydroxyl group content (% by weight) = {(XY) / X} × 100
Furthermore, examples of the carrier (c) that can be used in the present invention include granular or fine particle solids of organic compounds having a particle size in the range of 10 to 300 μm. Examples of these organic compounds include (co) polymers, vinylcyclohexane and styrene, which are mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Examples thereof include a polymer or copolymer produced as a main component.
Furthermore, 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 As the organoaluminum compound (hereinafter sometimes referred to as "component (d)") used as necessary in the present invention, for example, the following general formula (i) ) Can be exemplified.

R ¹ _n AlX _3-n (i)
(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X 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, such as an alkyl group, a cycloalkyl group, or an aryl group. Group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of the (d) organoaluminum compound 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, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.
In addition, as the (d) organoaluminum compound, a compound represented by the following general formula (ii) can also be used.

R ¹ _n AlY _3-n (ii)
(In the formula, R ¹ is the same as above, and Y is —OR ² group, —OSiR ³ ₃ group, —OAlR ⁴ ₂ group, —NR ⁵ ₂ group, —SiR ⁶ ₃ group or —N (R ⁷ ). a AlR ⁸ ₂ group, n is ^{1~2, R 2, R 3,} R 4 and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, R ⁵ Are a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ⁶ and R ⁷ are a methyl group, an ethyl group, etc.) Includes the following compounds.

(1) Compounds represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide,
(2) Compounds represented by R ¹ _n Al (OSiR ³ ₃ ) _3-n , such as Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al ( OSiEt ₃ ) etc .;
(3) a compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ ,
(Iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc .;
(4) Compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ Al
NHMe, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (Si
Me ₃ ) ₂ etc .;
(5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , for example, (iso-Bu) ₂ AlSiMe ₃
Such;
(6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n represented by a compound such as Et ₂ AlN (Me
) AlEt _2, such as _{(iso-Bu) 2 AlN (} Et) Al (iso-Bu) 2.
Among the organoaluminum compounds represented by the general formulas (i) and (ii), the general formula R ¹ ₃
A compound represented by Al, R ¹ _n Al (OR ² ) _3-n , R ¹ _n Al (OAlR ⁴ ₂ ) _3-n is preferable, and a compound in which R ¹ is an isoalkyl group and n = 2 is particularly preferable. .

The olefin polymerization catalyst (Cat-1) is formed from the above components (a) and (b) and, if necessary, the component (d). ) (Solid catalyst (Cat-2)) is a solid catalyst (component) in which component (a) and component (b) as described above are supported on carrier (c), and component (d) as necessary. Formed from.

FIG. 1 shows a process for preparing an olefin polymerization catalyst (Cat-1).
The olefin polymerization catalyst (Cat-1) can be prepared by mixing and contacting each catalyst component inside or outside the polymerization vessel. However, after component (a) is 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 catalyst for olefin polymerization (Cat-1) can be formed by mixing and contacting the component (a), the component (b), and, if necessary, the component (d) in an inert hydrocarbon solvent. The contact order of each component is arbitrarily selected, but when component (a) and component (b) are mixed and contacted, it is preferable to add component (b) to the suspension of component (a). Component (b) is prepared by mixing two or more transition metal compounds (components (b-I) and (b-II)) that form component (b) in advance and then bringing them into contact with other components. Is preferred.

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

When the component (a) and the component (b) are mixed and contacted as necessary, the concentration of the component (a) is about 0.1 to 5 mol in terms of aluminum in the component (a). / Liter (solvent), preferably in the range of 0.3 to 3 mol / liter (solvent). The atomic ratio (Al / transition metal) between aluminum (Al) in component (a) and the transition metal in component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a) used as necessary
/ Al-a) is usually in the range of 0.02 to 3, preferably 0.05 to 1.5. Ingredient (a
) And component (b), and if necessary, the mixing temperature when mixing and contacting component (d) is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 minute to 50 hours. It is preferably 10 minutes to 25 hours.

The olefin polymerization catalyst (Cat-1) prepared as described above has a component (b) of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol in terms of transition metal atom per 1 g of the catalyst, preferably It is contained in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ mol, and the component (a) and the component (d) are 10 ^{−2 to} 2.5 × 10 ⁻² mol, preferably 1. desirably it is contained in an amount of 5 × 10 ^-2 ~2 × 10 ^-2 mol.

The solid catalyst (Cat-2) can be prepared by supporting the component (a) and component (b) as described above and, if necessary, the component (d) on the 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) is arbitrarily selected. (C) is mixed and contacted, then component (b) is mixed and contacted, and if necessary, component (d) is mixed and contacted. Component (b) is prepared by mixing two or more transition metal compounds forming component (b), components (b-I) and (b-II)), and then bringing them into contact with other components. Is preferred.
The contact of the component (a), the component (b), the carrier (c) and the component (d) can be performed in an inert hydrocarbon solvent. Examples thereof include an inert hydrocarbon solvent used in the preparation of the olefin polymerization catalyst (Cat-1) described above.

When the component (a), the component (b) and the carrier (c) and, if necessary, the component (d) are mixed and contacted, the component (b) is usually converted into a transition metal atom per 1 g of the carrier (c). It is used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, and the concentration of component (b) is about 10 ⁻⁴ to 2 × 10 ⁻² mol. / Liter (solvent), preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / liter (solvent). The atomic ratio (Al / transition metal) between aluminum (Al) in component (a) and the transition metal in component (b) is usually 10 to 500, preferably 20 to 200. Aluminum atom (Al-d) in component (d) and component (d) used as necessary
The atomic ratio (Al-d / Al-a) of aluminum atoms (Al-a) in a) is usually 0.02 to 3,
Preferably it is the range of 0.05-1.5. The mixing temperature when the component (a), the component (b) and the carrier (c) and, if necessary, the component (d) are mixed and contacted is usually −50 to 150 ° C., preferably −20 to 120 ° C., The contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

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

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

  As the prepolymerization catalyst, an olefin may be introduced into the suspension prepared from the above-mentioned solid catalyst (Cat-2) (solid catalyst component), and the solid produced after preparing the solid catalyst (Cat-2). The catalyst (Cat-2) may be separated from the suspension, and then the solid catalyst (Cat-2) may be suspended again with an inert hydrocarbon, and the olefin may be introduced thereto.

In preparing the prepolymerization catalyst, the component (b) is usually 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent) in terms of the transition metal atom in the component (b), preferably It is used in an amount of 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the component (b) is usually 5 × 10 ^{−6 to} 5 × 10 in terms of transition metal atom per 1 g of the carrier (c). It is used in an amount of ^-4 mol, preferably 10 ^-5 to 2 x 10 ^-4 mol. The atomic ratio (Al / transition metal) of aluminum in component (a) and transition metal in component (b) is usually 10 to 500, preferably 20 to 200. 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 necessary is usually 0. 02-3, preferably 0.05-1.
The range is 5.

The solid catalyst component is usually in an amount of 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent) as a transition metal in the transition metal compound. Used.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.
Examples of the olefin used in the prepolymerization include ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. 1-decene, 1-dodecene, 1-tetradecene and the like. Among these, ethylene or a combination of ethylene and an α-olefin used for polymerization is particularly preferable.

  The prepolymerization catalyst is prepared, for example, as follows. That is, the support is suspended with an inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to the suspension and allowed to react for a predetermined time. The supernatant is then removed and the resulting solid component is resuspended with inert hydrocarbons. A transition metal compound (component (b)) is added to the system and reacted for a predetermined time, and then the supernatant is removed to obtain a solid catalyst component. Subsequently, the prepolymerized catalyst is obtained by adding the solid catalyst component obtained above to the inert hydrocarbon containing the organoaluminum compound (component (d)) and introducing the olefin into the solid catalyst component.

  In the prepolymerization, the amount of the olefin polymer to be produced is desirably 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).

In the prepolymerization catalyst, the component (b) per gram of the support (c) is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ in terms of transition metal atoms. The aluminum atom (Al) in the component (a) and the component (d) is supported in a molar amount, and the molar ratio (Al / M) to the transition metal atom (M) in the component (b) is 5 to 200. It is desirable that it is supported in an amount in the range of 10 to 150.

The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure. In the prepolymerization, the preliminary viscosity [η] measured in decalin at least 135 ° C. in the presence of hydrogen is in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g. It is desirable to produce a polymer.
In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase, preferably in the gas phase, in the presence of the olefin polymerization catalyst as described above. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or 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, methylcyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as gasoline, kerosene and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When the slurry polymerization method or the gas phase polymerization method is used, the catalyst as described above is usually 10 ⁻⁸ to 10 ⁻³ mol / liter, preferably 10 ⁻ as the transition metal atom concentration in the polymerization reaction system. It is preferably used in an amount of ⁷ to 10 ^-4 mol / liter.

  In the olefin polymerization catalyst formed from the component (a) and the component (b), and if necessary, the component (d), an aluminum atom (Al) in the component (d) used as necessary, and a transition The atomic ratio (Al / M) with the transition metal atom (M) in the metal compound (b) is in the range of 5 to 300, preferably 10 to 200, more preferably 15 to 150.

  In the olefin polymerization catalyst formed from the component (a), the component (b) and the carrier (c) and, if necessary, the component (d), an organoaluminum oxy compound (component) supported on the carrier at the time of polymerization. In addition to (a)), an unsupported organoaluminum oxy compound may be used. In this case, the atomic ratio (Al / M) of 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 Is in the range of 10 to 200, more preferably 15 to 150. The component (d) used as necessary may be supported on the carrier (c) or may be added during the polymerization. Furthermore, the component (d) is supported on the carrier (c) and may be added during the polymerization. At this time, the component (d) supported on the carrier and the component (d) added in the polymerization may be the same or different. The atomic ratio (Al / M) of the aluminum atom (Al) in the component (d) used as necessary and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably The range is 10 to 200, more preferably 15 to 150.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is The range is usually 0 to 120 ° C., preferably 20 to 100 ° C.
The polymerization pressure is usually from atmospheric pressure 100 kg / cm ^2, and preferably a pressurized condition of to 50 kg / cm ^2, the polymerization is a batch, semi-continuous, be carried out by any of the methods of continuous it can.

  Furthermore, the polymerization can be performed 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 by such an olefin polymerization catalyst include ethylene and α-olefins having 6 to 8 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1- Α-olefins such as pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5 -Methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene . Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

  In the ethylene / α-olefin copolymer obtained by the olefin polymerization method of the present invention, 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 from 70 to 96% by weight, and the 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 2%. It is desirable to be present in an amount of 35% by weight, most preferably 4-30% by weight.

The ethylene / α-olefin copolymer thus obtained preferably has the characteristics shown in the above-mentioned (Ai) to (A-iii), excellent in moldability, excellent in transparency and mechanical strength. Film can be manufactured.
Ethylene copolymer composition (A ')
The ethylene-based copolymer composition (A ′) according to the present invention has substantially the same composition and utility as the ethylene / α-olefin copolymer (A),
It consists of an ethylene / α-olefin copolymer (B) and a different ethylene / α-olefin copolymer (C).
The 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 are the same as those described above.

  In the ethylene / α-olefin copolymer (B), 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, and most preferably 70 to 96%. The structural unit present in an amount of% by weight and 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, and particularly preferably 4%. It is desirable to be present in an amount of ˜30% by weight.

The ethylene / α-olefin copolymer (B) preferably has the following characteristics (Bi) to (B-vii), and the following (Bi) to (B-viii) It is particularly preferable to have the characteristics shown in FIG.
(Bi) The density (d) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0.935 g / cm ³ , most Preferably it is in the range of 0.905 to 0.930 g / cm ³ .
(B-ii) The melt flow rate (MFR) is in the range 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.

(B-iii) When the n-decane soluble component fraction [W (wt%)] and density [d (g / cm ³ )] at 23 ° C. are MFR ≦ 10 g / 10 min,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 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
The relationship indicated by is satisfied.
(B-iv) The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
The relationship indicated by is satisfied.

  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), the n-decane soluble component amount fraction (W) and the density (d) It can be said that the ethylene / α-olefin copolymer (B) having a relationship as described above has a narrow composition distribution.

( ^Bv ) 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 relationship indicated by is satisfied.

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

(B-vii) 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 <Mw / Mn <3.0
It is in the range.

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 is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and BHT ( Takeda Pharmaceutical Co., Ltd.) was used at 0.025% by weight, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as the detector. Standard polystyrenes were manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and pressure chemicals were used for 1000 <Mw <4 × 10 ⁶ .

(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.
The unsaturated bond was quantified by using ¹³ C-NMR, a signal attributed to other than the double bond, ie, a signal in the range of 10 to 50 ppm, and a signal attributed to the double bond, ie, in the range of 105 to 150 ppm. The area intensity of the signal is determined from the integral curve and determined from the ratio.

The ethylene / α-olefin copolymer (B) is, for example, in the presence of an olefin polymerization catalyst containing (a) an organoaluminum oxy compound and (b-II) a transition metal compound represented by the general formula (II). It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms. The (a) organoaluminum oxy compound and (b-II) transition metal compound are the same as those described in the process for producing the ethylene / α-olefin copolymer (A). In the same manner as described above, the carrier (c) and the organoaluminum compound (d) may be used, and prepolymerization may be performed. The amount of each component used, the prepolymerization conditions, and the main polymerization conditions are the same as in the production of the ethylene / α-olefin copolymer (A).

  The 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 those described above.

In the ethylene / α-olefin copolymer (C) used in the present invention, 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, it is present in an amount of 70 to 96% by weight, and the 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 desirable that it is present in an amount of 4 to 30% by weight.
The ethylene / α-olefin copolymer (C) preferably has the following properties (Ci) to (Cv), and the following (Ci) to (C-vi): It is particularly preferable to have the characteristics shown in FIG.

(Ci) The density (d) is 0.880-0.970 g / cm ³ , preferably 0.880-0.960 g / cm ³ , more preferably 0.890-0.935 g / cm ³ , most Preferably it is in the range of 0.905 to 0.930 g / cm ³ .
(C-ii) The melt flow rate (MFR) is in the range 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.
(C-iii) When the n-decane soluble component fraction [W (% by weight)] and density [d (g / cm ³ )] at 23 ° 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
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
The relationship indicated by is satisfied.

(C-iv) The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
The relationship indicated by is satisfied.

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), the n-decane soluble component fraction (W) and the density (d) It can be said that an ethylene / α-olefin copolymer having a relationship as described above has a narrow composition distribution. ( ^Cv ) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 min)] MT ≦ 2.2 × MFR ^−0.84
Satisfies the relationship.

(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 an ethylene / α-olefin copolymer (C) includes, for example, (a) an organoaluminum oxy compound and (b-I) a transition metal compound represented by the general formula (I). It is obtained by copolymerizing ethylene and an olefin having 6 to 8 carbon atoms in the presence of. The (a) organoaluminum oxy compound and the (b-I) transition metal compound are the same as those described in the method for producing the ethylene / α-olefin copolymer (A). In the same manner as described above, the carrier (c) and the organoaluminum compound (d) may be used, and prepolymerization may be performed. The amount of each component used, the prepolymerization conditions, and the main polymerization conditions are the same as in the production of 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 wt%, preferably 2 to 80 wt%. It is desirable that the α-olefin copolymer (C) is contained in an amount of 10 to 99% by weight, preferably 20 to 98% by weight.

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

Particularly in the present invention, it is desirable that the ethylene / α-olefin copolymers (B) and (C) are both 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)] 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 relationship indicated by is satisfied.

The ethylene copolymer composition (A ′) having such characteristics has a melt tension (M
Since T) is high, the moldability is good.
(A′-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / mol K) obtained from the shift factor of time-temperature superposition of the flow curve, and copolymers (B) and (C) The relationship between the carbon number (C) of hexene-1 in the polymer and the total content (x mol%) of hexene-1 in the copolymers (B) and (C),
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1500) × x + 2.87
More preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1300) × x + 2.87
The relationship indicated by is satisfied.

(A′-iii) When a film having a thickness of 30 μm is produced from the ethylene copolymer composition (A ′) by inflation molding, the haze of the film satisfies the following relationship.

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

The ethylene-based copolymer composition (A ′) that satisfies such requirements is excellent in moldability and transparency of the resulting 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 / Mn, where Mw: weight average molecular weight,
Mn: number average molecular weight) is 2.0 ≦ Mw / Mn ≦ 2.5
Preferably 2.0 ≦ Mw / Mn ≦ 2.4
It is in the range.

Furthermore, in the ethylene-based copolymer composition (A ′) according to the present invention, 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, it is present in an amount of 70 to 96% by weight, and the structural unit derived from an α-olefin having 6 to 8 carbon atoms, preferably hexene-1, is 0 to 50% by weight, preferably 1 to 45% by weight, and more. Preferably it is present in an amount of 2 to 35% by weight, particularly preferably 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 , more preferably 0.890 to 0.9
35 g / cm ^3, and most preferably is desirably in the range of 0.905~0.930g / cm ^3.

The melt flow rate (MFR) of the ethylene copolymer composition (A ′) is 0.05-2.
It is desired to be in the range of 00 g / 10 minutes, preferably 0.08 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

The fraction of the n-decane soluble component at 23 ° C. [W (wt%)] and the density [d (g / cm ³ )] of the ethylene copolymer composition (A ′) at MFR ≦ 10 g / 10 min. When,
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
It is desirable to satisfy the relationship indicated by.

The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve of the ethylene copolymer composition (A ′) measured by a differential scanning calorimeter (DSC).
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
It is desirable to satisfy 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), the n-decane soluble component amount fraction (W) and the density (d) It can be said that the ethylene-based copolymer composition (A ′) having a relationship as described above has a narrow composition distribution.

The ethylene-based copolymer composition (A ′) comprising the ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C) is produced using a known method. For example, it can be manufactured by the following method.

(1) Ethylene / α-olefin copolymer (B), ethylene / α-olefin copolymer (C), and other components added as required are mechanically used using a tumbler, an extruder, a kneader or the like. Blending or melt mixing.
(2) Ethylene / α-olefin copolymer (B), ethylene / α-olefin copolymer (C), and other components to be added as required are mixed with a suitable good solvent (for example, hexane, heptane, decane, A hydrocarbon solvent such as cyclohexane, benzene, toluene and xylene), and then the solvent is removed.
(3) Prepare solutions in which ethylene / α-olefin copolymer (B), ethylene / α-olefin copolymer (C), and other components added as required are separately dissolved in an appropriate good solvent. And then mixing and then removing the solvent.
(4) A method of combining the methods (1) to (3) above.

As described above, both the ethylene / α-olefin copolymer (A) and the ethylene copolymer composition (A ′) according to the present invention are excellent in moldability, transparency and mechanical strength. Although excellent films can be produced, they can be used in combination with other polymers, preferably ethylene / α-olefin copolymers. 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 is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-
Examples include hexadecene, 1-octadecene, and 1-eicosene.

  In the ethylene / α-olefin copolymer (D), 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, and most preferably 70 to 96%. The constituent unit present in an amount of% by weight and derived from an α-olefin having 3 to 20 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, most preferably 4 It is desirable to be present in an amount of ˜30% by weight.

  Such an 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).

(Di) The density (d) is 0.850 to 0.980 g / cm ³ , preferably 0.910 to 0.960 g / cm ³ , more preferably 0.915 to 0.955 g / cm ³ , most Preferably it exists in the range of 0.920-0.950g / cm < ³ >.

(D-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 0.4 to 1.25 dl / g, more preferably 0.5 to 1.23 dl / g. It is in the range of g. (D-iii) The temperature (Tm (° C.)) and density (d (g / cm ³ )) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC).
Tm <400 × d−250
Preferably Tm <450 × d-297
More preferably, Tm <500 × d-344
Particularly preferably, Tm <550 × d−391
It is desirable to satisfy the relationship indicated by.

(D-iv) When the n-decane soluble component amount fraction (W (% by weight)) and the density (d (g / cm ³ )) 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
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
The relationship indicated by is satisfied.

  Thus, the relationship between the temperature (Tm) and the density (d) at the maximum peak position in the endothermic curve measured by the differential scanning calorimeter (DSC), the n-decane soluble component fraction (W) and the density ( It can be said that the ethylene / α-olefin copolymer (D) having the above relationship with d) 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 ethylene / It is not the same as the α-olefin copolymer (D). Specifically, the ethylene / α-olefin copolymer (D) and the ethylene / α-olefin copolymers (A) to (C) can be distinguished in the following characteristics.

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

  Furthermore, the ethylene / α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (C-iii) to (Cv) that define the copolymer (C).

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

Hereinafter, the transition metal compound (b-III) will be described.
(B-III) Transition metal compound (b-III) The periodic table containing a ligand having a cyclopentadienyl skeleton used in the production of the ethylene / α-olefin copolymer (D) The Group 4 transition metal compound (hereinafter sometimes referred to as “component (b-III)”) is a Group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton. Although it does not specifically limit, It is preferable that it is a transition metal compound shown 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, preferably zirconium.

X is the valence of the transition metal.
L ³ is a ligand coordinated to the transition metal atom M, at least one L ³ is a ligand having a cyclopentadienyl skeleton, and as a ligand having a cyclopentadienyl skeleton, For example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group Alkyl substituted cyclohexane such as methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group Pentadienyl group or indenyl group, 4,5,6,7-tetrahi Roindeniru group, and the like can be exemplified 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 preferable.
The compound represented by the general formula (III) is a ligand having a cyclopentadienyl skeleton 2
When two or more are included, the ligands having two cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

In the general formula (III), L ³ other than the ligand having a cyclopentadienyl skeleton is used.
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom, a hydrogen atom, or a SO ₃ R group (wherein L ¹ is the same as L ¹ in the general formula (I)). R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.

The transition metal compound represented by the general formula (III) is more specifically represented by the following general formula (III ′) when the valence of the transition metal is 4, for example.
R ² _k R ³ _l R ⁴ _m R ⁵ _n M (III ′)

(Wherein M is the transition metal atom, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO ₃ R group, a halogen atom or a hydrogen atom, k is an integer of 1 or more, and k + 1 + m + n = 4 is there.)

In the present invention, a metallocene compound in which one of R ³ , R ⁴ and R ⁵ is a group (ligand) having a cyclopentadienyl skeleton, for example, R ² and R ³ are cyclopentadienyl. A metallocene compound which is a group having a skeleton (ligand) is preferably used. These groups having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. May be connected via each other. In this case, other ligands (for example, R ⁴ and R ⁵ ) are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups. , SO ₃ R, a 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, ethylenebis (indenyl) ) Diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (indenyl) zirconium bis ( p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (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 (dimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) di Konium 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) methylzirconium Monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride Lido, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride Bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) Zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate) Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride Bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium Dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (meth Rubutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, Examples include bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.

In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. . Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.
In addition, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be used.

The transition metal compound represented by the general formula (III) includes the transition metal compound (b-I) represented by the general formula (I) and the transition metal compound (b) represented by the general formula (II). -II) is included.

The ethylene / α-olefin copolymer (D) comprises ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst, and the density of the resulting copolymer is 0.850 to 0. It can be produced by copolymerizing to 980 g / cm ³ .
The ethylene / α-olefin copolymer (D) is preferably 9 with respect to 100 parts by weight of the above-mentioned ethylene / α-olefin copolymer (A) or ethylene copolymer composition (A ′).
9 to 60 parts by weight, more preferably 95 to 60 parts by weight.

The composition of the ethylene / α-olefin copolymer (D) and the above-described ethylene / α-olefin copolymer (A) or ethylene copolymer composition (A ′) is a known method already described. Can be manufactured. Moreover, it can manufacture also by the multistage polymerization method which divided the copolymerization into two or more steps from which reaction conditions differ using one or several superposition | polymerization devices.

The ethylene / α-olefin copolymer (A) and the ethylene copolymer composition (A ′) according to the present invention are not particularly limited in the field in which an ethylene copolymer has been used. Although it is used, it is particularly suitably used for films such as cast films and inflation films, and sheets such as extruded sheets. A film can be obtained by processing by ordinary air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding, or the like. The film thus formed is excellent in transparency and mechanical strength, and has heat sealing properties, hot tack properties, heat resistance, good blocking properties, etc., which are characteristics of ordinary LLDPE. Further, since the composition distribution of the ethylene / α-olefin copolymer or the ethylene copolymer composition is extremely narrow, there is no stickiness on the film surface. Further, since the melt tension is high, the bubble stability during inflation molding is excellent.

Films obtained by molding such an ethylene / α-olefin copolymer (A) and an ethylene copolymer composition (A ′) are standard bags, sugar bags, oil packaging bags, and water packaging. Suitable for various packaging films such as bags and agricultural materials. It can also be used as a multilayer film by being bonded to a base material such as nylon or polyester.

The method for producing an ethylene / α-olefin copolymer according to the present invention comprises:
(A) an organoaluminum oxy compound, (b-I) a transition metal compound, and (b-II)
In the presence of an olefin polymerization catalyst comprising a transition metal compound, ethylene and an α-olefin having 6 to 8 carbon atoms are copolymerized.

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

  The ethylene / α-olefin copolymer and the ethylene copolymer composition of the present invention have high melt tension and excellent moldability. A film excellent in transparency and mechanical strength can be produced from such an ethylene / α-olefin copolymer and an ethylene copolymer composition.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the present invention, the physical properties of the film were evaluated as follows.

[Haze (Haze)]
Measured according to ASTM-D-1003-61.
[Gloss]
It measured according to JIS Z8741.

[Dirt impact strength]
Measured according to ASTM D 1709 A method.

[Preparation Example 1]
[Preparation of catalyst components]
After 5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene, it was cooled to 0 ° C. Thereafter, 28.7 liters of a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) 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, then heated to 95 ° C. over 1.5 hours, and reacted 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. To this system, 20.0 liters of a toluene solution (Zr; 14.0 mmol / liter) of bis (methylcyclopentadienyl) zirconium dichloride was added dropwise at 80 ° C. over 30 minutes, and further reacted at 80 ° C. for 2 hours. It was. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst]
By adding 0.85 kg of the solid catalyst obtained above and 77 g of 1-hexene to 85 liters of hexane containing 1.7 mol of triisobutylaluminum, and prepolymerizing ethylene at 35 ° C. for 3.5 hours, A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[polymerization]
Copolymerization of ethylene and 1-hexene was performed using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. In order to maintain a constant gas composition during polymerization by continuously supplying the prepolymerized catalyst prepared above at a rate of 0.05 mmol / h in terms of zirconium atom and 10 mmol / h of triisobutylaluminum, ethylene, 1-hexene Then, hydrogen and nitrogen were continuously supplied (gas composition: 1-hexene / ethylene = 0.020, hydrogen / ethylene = 9.5 × 10 ⁻⁴ , ethylene concentration = 50%). The polymer yield was 4.1 kg / h. The obtained ethylene / α-olefin copolymer (B-1) was melt-kneaded and pelletized.

  The melt properties are shown in Table 1.

[Preparation Example 2]
[Preparation of catalyst components]
In [Preparation of catalyst component] in Preparation Example 1, instead of 20.0 liters of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter), bis (1,3-nbutyl The solid catalyst component was prepared in the same manner except that 8.2 liters of a toluene solution of methylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) was used.

[Preparation of prepolymerization 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 prepolymerization catalyst obtained in [Preparation of prepolymerization catalyst], the gas composition was 1-hexene / ethylene = 0.020, hydrogen / ethylene = 5.0 × 10 ⁻⁴ , and ethylene concentration = 50%. Except for this, an ethylene copolymer (C-1) was obtained in the same manner as in Preparation Example 1. The characteristics of the obtained ethylene copolymer (C-1) are shown in Table 1.

[Example 1]
[Preparation of catalyst components]
In [Preparation of catalyst component] in Preparation Example 1, instead of 20.0 liters of a toluene solution (Zr; 14.0 mmol / liter) of bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-n- 5. Toluene solution of butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and 5.8 liter of toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter) The solid catalyst component was prepared in the same manner except that 0 liter was used.

[Preparation of prepolymerization 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 [Preparation of prepolymerized catalyst], the gas composition was 1-hexene / ethylene = 0.020, hydrogen / ethylene = 4.5 × 10 ⁻⁴ , and ethylene concentration = 50%. Except for this, an ethylene copolymer (A-1) was obtained in the same manner as in Preparation Example 1. Table 1 shows the properties of the resulting ethylene copolymer (A-1).

[Example 2]
[polymerization]
An ethylene / α-olefin copolymer (MFR) was prepared in the same manner as in Example 1 except that the gas composition was adjusted so that the density was the ethylene / α-olefin copolymer (A-2) described in Table 1. A-2) was obtained.

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

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

[Comparative Example 2]
[Preparation of catalyst components]
In [Preparation of catalyst component] in Preparation Example 1, instead of 20.0 liters of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter), bis (1,3-dimethylcyclohexane) The solid catalyst component was prepared in the same manner except that 10.0 liters of a toluene solution (Zr; 28.0 mmol / liter) of pentadienyl) zirconium dichloride was used.

[Preparation of prepolymerization 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]
Except for using the prepolymerized catalyst obtained in the above [Preparation of prepolymerized catalyst] and preparing a gas composition so that the MFR and density are the ethylene / α-olefin copolymers (D) described in Table 1, In the same manner as in Preparation Example 1, an ethylene / α-olefin copolymer (D) was obtained.

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

[Examples 5 to 8]
And [Comparative Examples 3 and 4]

[Film forming]
Using an ethylene / α-olefin copolymer or an ethylene copolymer composition pellet shown in Table 3, an inflation film was obtained under the following conditions. Using a single screw extruder of 20 mmφ · L / D = 26, 25 mmφ die, lip width 0.7 mm, single slit air ring, air flow rate = 90 l / min, extrusion rate = 9 g / min, blow ratio = 1. 8. A film having a take-off speed of 2.4 m / min, a processing temperature of 200 ° C. and a thickness of 30 μm was obtained by inflation molding. Table 3 shows the film properties.

[Example 9]
In the same manner as in 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) described in Table 1, ethylene / α -Olefin copolymers (A-4) and (A-5) were produced. These ethylene / α-olefin copolymers (A-4) and (A-5) are melt-kneaded at a weight ratio (A-4) / (A-5) = 60/40 and pelletized to obtain an ethylene copolymer. A composition (L-1) was obtained. Using the pellets of the ethylene copolymer composition (L-1), an inflation film was obtained in the same manner as in Examples 5-8. The results are shown in Tables 2 and 3.

[Example 10]
Except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymer (A-6) described in Table 1, the ethylene / α-olefin copolymer ( A-6) was produced. The ethylene / α-olefin copolymer (A-6) and the ethylene / α-olefin copolymer (A-5) produced in Example 9 were in a 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), an inflation film was obtained in the same manner as in Examples 5-8. The results are shown in Tables 2 and 3.

[Example 11]
Except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymers (A-7) and (A-8) described in Table 1, ethylene / α -Olefin copolymers (A-7) and (A-8) were produced. This ethylene / α-olefin copolymer (A-7), (A-8) is melt-kneaded at a weight ratio (A-7) / (A-8) = 60/40 and pelletized to form an ethylene copolymer. A composition (L-3) was obtained. By using pellets of this ethylene copolymer composition (L-3), an inflation film was obtained in the same manner as in Examples 5-8. The results are shown in Tables 2 and 3.

It is explanatory drawing which shows the preparation process of the catalyst for olefin polymerization used by this invention.

Claims (4)

(B) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Bi) The density is in the range of 0.880 to 0.970 g / cm ³ ,
(B-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(B-iii) Decane-soluble component amount ratio (W) and density (d) at room temperature,
When MFR ≦ 10g / 10min,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(B-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured with a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(Bv) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(B-vi) Flow activation energy ((E _a ) × 10 ⁻⁴ J / mol K) determined from the shift factor of time-temperature superposition of the flow curve, and the number of carbon atoms of the α-olefin in the copolymer (C)
And the α-olefin content (x mol%) in the copolymer
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(B-vii) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by GPC (Mw
/ Mn)
2.2 <Mw / Mn <3.5
An ethylene / α-olefin copolymer characterized by the following:
(C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Ci) the density is in the range of 0.880-0.970 g / cm ³ ,
(C-ii) The melt flow rate (MFR) at 190 ° C. and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(C-iii) Decane-soluble component amount ratio (W) at room temperature and density (d) are MFR ≦ 10
When g / 10 minutes
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(C-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
( ^Cv ) The melt tension (MT) at 190 ° C. and the melt flow rate (MFR) are MT ≦ 2.2 × MFR ^−0.84
An ethylene / α-olefin copolymer represented by:
An ethylene copolymer composition (A ′) comprising:
The ratio of the melt flow rate (MFR (C)) of (C) to the melt flow rate (MFR (B)) of (B) is 1 <(MFR (C)) / (MFR (B)) ≦ 20
An ethylene copolymer composition (A ′). The ethylene / α-olefin copolymers (B) and (C) are both ethylene / hexene-1 copolymers,
(A′-i) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A′-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / mol K) determined from the time-temperature superposition shift factor of the flow curve, and the copolymers (B) and (C) The relationship between the carbon number (C) of hexene-1 in the polymer 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 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A'-iii) When the copolymer composition is blow-molded to produce a film having a thickness of 30 μm, the haze of the film satisfies the following relationship: The ethylene-based copolymer composition (A ′) as described;
When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² are FI ≧ 100 × MFR
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 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 carbon number of hexene-1, that is, “6”). In addition to the requirements (A′-i) to (A′-iii), (A′-iv) the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by GPC (Mw
/ Mn)
2.0 ≦ Mw / Mn ≦ 2.5
The ethylene-based copolymer composition (A ′) according to claim 2, wherein (A ′) the ethylene copolymer composition according to claim 1;
(D)
(A) an organoaluminum oxy compound;
(B-III) ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton. Obtained by copolymerization,
(Di) The density is in the range of 0.850 to 0.980 g / cm ³ ,
(D-ii) an ethylene / α-olefin copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g (however, an ethylene / α-olefin copolymer) (B) and (C) and the ethylene / α-olefin copolymer (D) are not the same)
An ethylene copolymer composition comprising:

Images