JPH06136193A - Ethylene copolymer composition - Google Patents

Abstract

PURPOSE:To provide an ethylene copolymer compsn. improved in heat stability, moldability, transparency and blocking resistance, by using 2 kinds of specific ethylene-alpha-olefin copolymers and low-density PE prepd. by high-pressure radical polymn. CONSTITUTION:99-60wt.% compsn. comprising (A) 5-95wt.% ethylene-3-20C alpha-olefin copolymer having a density (d) of 0.880 to 0.940g/cm<3>, an intrinsic viscosity (zetaA, in decalin at 135 deg.C) of 1.0 to 10.0dl/g, a Tm vs. d relationship: Tm<400Xd-250 [wherein Tm ( deg.C) is a temp. at the maximum absorption peak measured with a differential scanning calorimeter], etc., and (B) 5-95wt.% ethylene-3-20C alpha-olefin copolymer with d=0.910 to 0.960g/cm<3>, zetaB=0.5 to 2.0dl/g, Tm<400Xd-250, etc., with the proviso that the A/B density ratio is at most l, zetaA/zetaB=0.890 to 0.955, etc., is, blended with (C) l-40wt.% low-density PE prepd. by high-pressure radical polymn. and having an MFR of 0.1 to 50g/10min, etc.

Description

Detailed Description of the Invention

[0001]

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

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when molding blown film at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform high-speed molding stably, an ethylene copolymer with a large melt tension relative to its molecular weight should be selected. Must. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer under extrusion under high shear is small from the economical viewpoint such as quality improvement of the molded article and reduction of power consumption during molding.

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

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

Among the Ziegler type catalyst systems, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded product such as a film is less sticky. However, for example, JP-A-60-35007 describes that an ethylene-based polymer obtained by using a zirconocene compound composed of a cyclopentadienyl derivative as a catalyst contains one terminal unsaturated bond per molecule. However, like the ethylene-based polymer obtained using the above chromium-based catalyst, it is expected that the thermal stability is poor. Further, since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Therefore, if an ethylene-based polymer having excellent melt tension, small stress in the high shear region, good thermal stability, excellent mechanical strength, and narrow composition distribution appears, its industrial use will be improved. The target value is extremely large.

As a result of intensive studies in view of such a situation, the present inventors have found that (a) a bidentate in which two groups selected from a specific indenyl group or a substitution product thereof are bonded via a lower alkylene group. A compound of a Group IV transition metal having a ligand or a compound of a Group IV transition metal containing a ligand having a specific cyclopentadienyl skeleton, and (b) an organoaluminumoxy compound An ethylene / α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing is excellent in melt tension and thermal stability, and It was found that the composition distribution was narrow. However, such an ethylene / α-olefin copolymer does not always have a good balance between melt tension and fluidity, and thus a problem may occur when it is extrusion-molded into a film. Therefore, as a result of further research, ethylene / α obtained by blending two kinds of ethylene / α-olefin copolymers obtained by using the above-mentioned catalyst, which have different densities and MFRs, respectively.
-The ethylene-based copolymer composition obtained by further blending the olefin copolymer composition with low-density polyethylene by the high-pressure radical method is excellent in thermal stability, melt tension and fluidity (FI) in a high shear region. And, it was found that the obtained film was excellent in transparency, mechanical strength and blocking resistance, and thus completed the present invention.

[0008]

OBJECT OF THE INVENTION It is an object of the present invention to provide an ethylene-based copolymer composition capable of producing a film having excellent heat stability and moldability, transparency and blocking resistance.

[0009]

SUMMARY OF THE INVENTION An ethylene-based copolymer composition according to the present invention is a copolymer of [I] (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A- ii) The density (d) is in the range of 0.880 to 0.940 g / cm ³ , and (A-ii
i) The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is in the range of 1.0 to 10.0 dl / g, and (A-iv) of the endothermic curve measured by a differential scanning calorimeter (DSC). The temperature (Tm (° C.)) at the maximum peak position and the density (d) satisfy the relationship represented by Tm <400 × d-250, and (A-v) melt tension (MT (g)) at 190 ° C. and melt Flow rate (MFR)
^Satisfy the relationship ^represented by MT> 2.2 × MFR ^−0.84 , and (A-vi) 190 of the melt polymer.
Fluidity index (FI) defined by the shear rate when the stress at ℃ reaches 2.4 × 10 ⁶ dyne / cm ^2.
(1 / sec)) and the melt flow rate (MFR) satisfy the relationship represented by FI> 75 × MFR, and (A-vii) decane-soluble part (W (wt%)) and density (d) at room temperature. And an ethylene / α-olefin copolymer [A] of 5 to 95% by weight satisfying the relationship of W <80 × exp (−100 (d−0.88)) + 0.1, and (Bi) A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms,
(B-ii) Density (d) is 0.910 to 0.960 g / cm ^3.
(B-iii), the intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is in the range of 0.5 to 2.0 dl / g, and (B-iv) the differential scanning calorimeter ( Temperature at the maximum peak position of the endothermic curve measured by DSC (Tm (° C))
And the density (d) satisfy the relationship represented by Tm <400 × d-250, and (B-v) the decane-soluble part (W (wt%)) at room temperature and the density (d) have MFR ≦ 10.
When g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (-100 (D-
0.88)) + 0.1, wherein the ethylene / α-olefin copolymer composition [B] is 5 to 95% by weight, and the ethylene / α-olefin copolymer composition comprises (i) The ratio ([A] / [B]) between the density of the ethylene / α-olefin copolymer [A] and the density of the ethylene / α-olefin copolymer [B] is less than 1, ) The ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] is 1 or more. And (iii) the density of the composition is in the range of 0.890 to 0.955 g / cm ³ , and (iV) the melt flow rate (MFR) of the composition at 190 ° C. and a load of 2.16 kg is 0. .1-10
An ethylene / α-olefin copolymer composition having a range of 0 g / 10 minutes, and [II] a low density polyethylene by a high pressure radical method, wherein (i) the melt flow rate (MFR) is 0.1 to 5
Within the range of 0 g / 10 minutes, (ii) the molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MF) measured by GPC.
R) and high-pressure radical method low-density polyethylene satisfying the relationship represented by Mw / Mn ≧ 7.5 × log (MFR) -1.2, and the above ethylene / α-olefin copolymer composition [I] And the weight ratio ([I]: [II]) of the high-pressure radical method low-density polyethylene [II] is 99: 1 to 6
It is characterized by being in the range of 0:40.

The ethylene-based copolymer composition of the present invention can produce a film having excellent heat stability and moldability, transparency and blocking resistance.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The ethylene copolymer composition according to the present invention will be described in detail below. The ethylene-based copolymer composition according to the present invention is an ethylene / α-olefin copolymer composition comprising an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B]. , High-pressure radical method and low-density polyethylene.

[Ethylene / α-olefin copolymer [A]] The ethylene / α-olefin copolymer [A] constituting the ethylene copolymer composition according to the present invention comprises ethylene and 3 to 20 carbon atoms. Is a random copolymer with α-olefin. 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-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

Ethylene / α-olefin copolymer [A]
Then, the structural unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7
The structural unit that is present in an amount of 0 to 96% by weight and is derived from an α-olefin having 3 to 20 carbon atoms is 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight.
Is preferably present in an amount of.

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

Such an ethylene / α-olefin copolymer [A] has the following characteristics (A-ii) to (A-vii). (A-ii) Density (d) is 0.880 to 0.940 g / cm
³ , preferably 0.890 to 0.935 g / cm ³ , and more preferably 0.900 to 0.930 g / cm ³ .

The density (d) is 2.90 at 190.degree.
The strand obtained at the time of measuring the melt flow rate (MFR) under a load of 16 kg was heat treated at 120 ° C. for 1 hour, and
After slowly cooling to room temperature over time, measurement is performed with a density gradient tube.

(A-iii) The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is 1.0 to 10.0 dl / g, preferably 1.25 to 8 dl / g, more preferably 1.27.
It is preferably in the range of ˜6 dl / g.

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

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(° C) is 10 ° C /
It is obtained from the endothermic curve when the temperature is raised to 200 ° C. in minutes, the temperature is kept at 200 ° C. for 5 minutes, the temperature is lowered to room temperature at 20 ° C./min, and then the temperature is raised at 10 ° C./min. For the measurement, a DSC-7 type device manufactured by Perkin Elmer was used.

(Av) Melt tension at 190 ° C. (MT
(G)) and the melt flow rate (MFR) satisfy the relationship ^represented by MT> 2.2 × MFR ^−0.84 .

Such ethylene used in the present invention
The α-olefin copolymer [A] has a large melt tension (MT) and good moldability. The melt tension (MT
(G)) is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is,
The produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample. Using an MT measuring instrument manufactured by Toyo Seiki Seisakusho, resin temperature 190 ° C., extrusion speed 15 mm / min, winding speed 10 to 20 m / min, nozzle Diameter 2.09mmφ,
The nozzle length was 8 mm. When pelletizing,
To the ethylene / α-olefin copolymer [A], 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n- as a heat stabilizer were previously prepared. Octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate was added in an amount of 0.1% by weight, and calcium stearate as a hydrochloric acid absorbent was added in an amount of 0.05% by weight.

(A-vi) The stress at 190 ° C. is 2.4 ×
The fluidity index (FI (1 / sec)) and the melt flow rate (MFR) defined by the shear rate when reaching 10 ⁶ dyne / cm ² are FI> 75 × MFR, preferably FI> 100 × MFR. More preferably, it is desirable that the relationship represented by FI> 120 × MFR is satisfied.

Ethylene / α-olefin copolymer [A] in which FI and MFR satisfy the above relationship.
Since the low stress is maintained up to a high shear rate, the processing torque is small and the formability is good.

Fluidity index (FI) is 190 ° C
It is defined as the shear rate at which the shear stress at reaches 2.4 × 10 ⁶ dyne / cm ² . The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using a sample similar to MT measurement, using a capillary flow characteristic tester manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C. and a shear stress range of 5 × 10 ^{4 to} 3 × 10 ⁶ dyn
It is measured at about e / cm ² .

The MFR of the resin to be measured (g / 10
Min), and change the diameter of the nozzle as follows. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR (A-vii) n-decane at room temperature Fraction of soluble component (W
(Wt%)) and the density (d) are W <80 × exp (−100 (d−0.88)) + 0.1, preferably W <60 × exp (−100 (d−0.8)
8)) + 0.1, more preferably W <40 × exp (−100 (d−0.8)
8)) + 0.1 is satisfied.

The amount of n-decane soluble component (the smaller the amount of soluble component, the narrower the composition distribution) was measured by measuring about 3% of the copolymer.
g to 450 ml of n-decane, dissolved at 145 ° C., cooled to room temperature, the n-decane-insoluble part is removed by filtration, and the n-decane-soluble part is recovered from the filtrate.

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

Further, the ethylene / α-olefin copolymer [A] has the number of unsaturated bonds present in the molecule of not more than 0.5 per 1000 carbon atoms, and 1 per molecule of the polymer. It is desirable to be less than.

The unsaturated bond is quantified by ¹³ C-NMR.
Is used to identify signals other than double bonds, ie, 10
The area intensity of the signal in the range of ˜50 ppm and the signal attributed to the double bond, that is, the signal in the range of 105 to 150 ppm is determined from the integral curve and determined from the ratio.

Ethylene / α-having the above characteristics
The olefin copolymer [A] is a catalyst for olefin polymerization formed from (a) a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier described below, and (d) an organoaluminum compound if necessary. It can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence so that the resulting copolymer has a density of 0.880 to 0.940 g / cm ^3. .

[Ethylene / α-olefin copolymer [B]] The ethylene / α-olefin copolymer [B] constituting the ethylene copolymer composition according to the present invention comprises ethylene and 3 to 20 carbon atoms. Is a random copolymer with α-olefin. 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-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

Ethylene / α-olefin copolymer [B]
Then, the structural unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7
The structural unit that is present in an amount of 0 to 96% by weight and is derived from an α-olefin having 3 to 20 carbon atoms is 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight.
Is preferably present in an amount of.

The ethylene / α-olefin copolymer [B] has the following characteristics (B-ii) to (Bv). (B-ii) Density (d) is 0.910 to 0.960 g / cm
³ , preferably 0.915 to 0.955 g / cm ³ , and more preferably 0.920 to 0.950 g / cm ³ .

(B-iii) The intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is 0.5 to 2.0 dl / g, preferably 0.55 to 1.9 dl / g, and more preferably 0.1. 6
It is preferably in the range of to 1.8 dl / g.

(B-iv) Temperature (T) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC)
m (° C.)) and the density (d) are as follows: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550 × d-391. It is desirable to meet the relationships shown.

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

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

Further, in the ethylene / α-olefin copolymer [B], the number of unsaturated bonds present in the molecule is not more than 0.5 per 1000 carbon atoms, and 1 per molecule of the polymer. It is desirable to be less than.

Ethylene / α-having the above characteristics
The olefin copolymer [B] has the following (a ′)
In the presence of a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier, and optionally (d) an organoaluminum compound-forming catalyst for olefin polymerization, ethylene and α- having 3 to 20 carbon atoms are used. With olefins,
The density of the obtained copolymer is 0.910 to 0.960 g / c.
It can be produced by copolymerizing so as to have m ³ .

The ethylene / α-olefin copolymer [A] which constitutes the ethylene-based copolymer composition according to the present invention,
[B] is in the presence of the following (a) transition metal compound, (b) organoaluminum oxy compound and (c) carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound, Ethylene and 3 to 20 carbon atoms
It can be produced by copolymerizing with the α-olefin of the above under the conditions described below.

The (a) transition metal compound (hereinafter sometimes referred to as “component (a)”) used in the present invention has two lower groups selected from a specific indenyl group or a substituted product thereof. Periodic table having bidentate ligands bonded via alkylene groups Group IVB transition metal compounds or specific substituted cyclopentadienyl groups as ligands
The compound is a group IVB transition metal compound, specifically a transition metal compound represented by the following formula [I] or [II].

MKL ¹ _X-2 ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the periodic table, and K and L ¹ are ligands coordinated to a transition metal atom. The ligand K is a bidentate ligand in which the same or different indenyl groups, substituted indenyl groups or partial water additives thereof are bonded via a lower alkylene group,
The ligand L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is a valence of the transition metal atom M. ML ² _X ... [II] (In the formula [II], M is a transition metal selected from Group IVB of the periodic table, and L ² is a ligand that coordinates to a transition metal atom. At least two ligands L
² is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group,
The ligand L ² other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is a transition metal atom M. Is the valence of. In the above general formula [I], M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

K is a ligand coordinating to a transition metal atom, and the same or different indenyl group, substituted indenyl group, or partial water additive of indenyl group or substituted indenyl group is bonded via a lower alkylene group. Bidentate ligand.

Specifically, ethylenebisindenyl group, ethylenebis (4,5,6,7-tetrahydro-1-indenyl)
Group, ethylenebis (4-methyl-1-indenyl) group, ethylenebis (5-methyl-1-indenyl) group, ethylenebis (6-methyl-1-indenyl) group, ethylenebis (7-methyl-1-) An indenyl) group can be illustrated.

L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom. As the hydrocarbon group having 1 to 12 carbon atoms, an alkyl group, a cycloalkyl group,
Examples thereof include an aryl group and an aralkyl group,
More specifically, methyl group, ethyl group, n-propyl group,
Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group;
Examples thereof include 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 neofil group.

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

Examples of the aryloxy group include a phenoxy group and the like. Halogen atom is fluorine,
Chlorine, bromine and iodine. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Examples of the transition metal compound represented by the general formula [I] include ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,5,
6,7-Tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1- Indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium methoxychloride, ethylenebis (4-methyl-1-indenyl) zirconium ethoxy chloride, Ethylenebis (4-methyl-1-indenyl) zirconium butoxycyclolide, ethylenebis (4-methyl-1-indenyl) zirconium methoxide, ethylenebis (4-methyl-1-indenyl) zirconium methyl chloride, ethylenebis (4- Methyl-1-indenyl) zirconium dimethyl, Chirenbisu (4-methyl-1-indenyl) zirconium benzyl chloride, ethylene-bis (4-methyl-1-indenyl) zirconium dibenzyl, ethylenebis (4-methyl
-1-Indenyl) zirconium phenyl chloride, ethylenebis (4-methyl-1-indenyl) zirconium hydride chloride, and the like. In the present invention, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Among these transition metal compounds represented by the general formula [I], ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,
5,6,7-Tetrahydro-1-indenyl) zirconium dichloride is particularly preferred.

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

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

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

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

Among these transition metal compounds represented by the general formula [II], bis (1.3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride is particularly preferred.

In the present invention, the periodic table containing a ligand (a ') having a cyclopentadienyl skeleton, which is used in the copolymerization of the ethylene / α-olefin copolymer [B],
The Group IV transition metal compound (hereinafter sometimes referred to as “component (a ′)”) is a Group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton. Although not particularly limited, a transition metal compound represented by the following general formula [III] is preferable.

ML _x ... [III] [wherein M is a transition metal selected from Group IVB of the periodic table, L is a ligand that coordinates to the transition metal, and at least one L is cyclo L is a ligand having a pentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a trialkylsilyl group, an SO ₃ R group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom, and x is a transition It is the valence of the metal. The transition metal compound represented by the general formula [III] includes the transition metal compound represented by the general formula [I] (a-
I) and the transition metal compound (a-II) represented by the above general formula [II].

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

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [III] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are alkylene such as ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. 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, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group and a trifluoromethanesulfonato group. The metallocene compound containing such a ligand having a cyclopentadienyl skeleton 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 '] (In the formula, M is the above transition metal, and R ² is a group (ligand) having a cyclopentadienyl skeleton. And R ³ , 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 groups, halogens. Atom or hydrogen atom, k is an integer of 1 or more, and k + l + m + n = 4.) In the present invention, in the above general formula, at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² A metallocene compound in which R ³ and R ³ are groups (ligands) having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons 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. It may be connected via. R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group,
It is a trialkylsilyl group, SO ₃ R, a halogen atom or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), 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, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethyl silylene bis (methylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (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, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can also be used. As the compound (a ′) used in the present invention, the above-exemplified compounds can be used as a catalyst, but it is preferable to use the above-mentioned transition metal compound (a), among which the transition metal compound (a)
It is more preferable to use, as a catalyst, the compounds particularly preferably exemplified in. Further, it is particularly preferable to use a compound in which the compounds (a ′) and (a) are the same.

Next, the organoaluminum oxy compound (b) will be described. The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) used in the present invention may be a conventionally known benzene-soluble aluminoxane, and can be used in JP-A-2- 27
It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent No. 6807.

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

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution.

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

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

Specific examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride;
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

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

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

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

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

The carrier (c) (hereinafter sometimes referred to as "component (c)") used in the present invention is an inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 300 μm. A 200 μm granular or particulate solid is used. Among these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, Ba
O, ThO ₂ etc. or mixtures thereof, eg 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. can be illustrated. 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 .

The inorganic oxide contains a small amount of Na ₂ C.
O 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 ,
Carbonate such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
It does not matter if it contains sulfates, nitrates or oxides.

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

Further, as the carrier (c) which can be used in the present invention, a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 2 carbon atoms.
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers, and polymers or copolymers containing vinylcyclohexane or styrene as a main component.

The catalyst used in the present invention is formed from the above-mentioned (a) transition metal compound, (b) organoaluminum oxy compound and (c) carrier, and if necessary (d)
Organoaluminum compounds may be used.

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

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

Such an organoaluminum compound (d)
Specifically, the following compounds are used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (d), compounds represented by the following general formula [IV] can be used. R ¹ _n AlY _3-n ... [IV] (In the formula [IV], 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 ) AlR ⁸ ₂ group, n is 1 to
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, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) A compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like; (4) compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2
(5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ; (6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN
(Et) Al (iso-Bu) ₂ etc.

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

In the present invention, when the ethylene / α-olefin copolymers [A] and [B] are produced, the above-mentioned component (a), component (b) and component (c), and if necessary, A catalyst prepared by contacting the component (d) is used. The contacting order of the components (a) to (d) at this time is arbitrarily selected, but preferably the component (c) and the component (b) are mixed and contacted, and then the component (a) is mixed and contacted, Further, if necessary, the component (d) is mixed and brought into contact.

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

Component (a), component (b), component (c) and
And, if necessary, mixing and contacting the component (d),
Minute (a) is usually 5 × 10 per 1 g of component (c).^-6~ 5x
10 ^-FourMol, preferably 10^-Five~ 2 x 10^-FourIn molar amounts
The concentration of component (a) used is about 10^-Four~ 2 x 10^-2
Mol / liter, preferably 2 × 10^-Four-10^-2Mol /
It is in the liter range. Component (b) made of aluminum
Atomic ratio with transition metal in minute (a) (Al / transition metal)
Is usually 10 to 500, preferably 20 to 200
It Aluminum as the component (d) used as necessary
Atom (Al-d) and the aluminum atom of the component (b) (Al-
The atomic ratio (Al-d / Al-b) of b) is usually 0.02 to 3, preferably.
It is preferably in the range of 0.05 to 1.5. Ingredient (a)
Minute (b), component (c) and optionally component (d)
The mixing temperature at the time of mixing and contacting is usually -50 to 150 ° C,
The temperature is preferably −20 to 120 ° C., and the contact time is 1 minute to
It is 50 hours, preferably 10 minutes to 25 hours.

Ethylene.α-obtained as described above
The catalyst used in the production of the olefin copolymers [A] and [B] has 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom of the transition metal atom derived from the component (a) per 1 g of the component (c). It is preferably supported in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ gram atom, and 10 ^{−3 to} 5 × 10 ⁻² aluminum atoms derived from the component (b) and the component (d) per 1 g of the component (c). It is desirable to support gram atoms, preferably in an amount of 2 × 10 ⁻³ to 2 × 10 ⁻² gram atoms.

The catalyst used in the production of the ethylene / α-olefin copolymers [A] and [B] is the above-mentioned component (a), component (a '), component (b) and component (c).
Further, it may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of the component (d) if necessary.
The prepolymerization is carried out by the above-mentioned component (a), component (a '),
Component (b), component (c) and optionally component (d)
Can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of

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

In the prepolymerization, the above component (a) is
Usually 10 ^{−6 to} 2 × 10 ⁻² mol / liter, preferably 5
It is used in an amount of × 10 ^-5 to 10 ^-2 mol / liter, and the component (a) is usually 5 × 10 ^{-6 to} 5 × 1 per 1 g of the component (c).
It is used in an amount of 0 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. The atomic ratio (Al / transition metal) of aluminum of the component (b) and the transition metal in the component (a) is usually 10 to 5.
00, preferably 20 to 200. The atomic ratio (Al-d) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) that are used as necessary.
/ Al-b) is usually 0.02 to 3, preferably 0.05 to
It is in the range of 1.5. The prepolymerization temperature is -20 to 80 ° C,
The temperature is preferably 0 to 60 ° C., and the prepolymerization time is 0.1.
It is about 5 to 100 hours, preferably about 1 to 50 hours.

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

The olefin polymer produced by the prepolymerization is
0.1-500 g, preferably 0.2 per 1 g of carrier (c)
It is desirable that the amount is ˜300 g, more preferably 0.5 to 200 g. Further, in the prepolymerization catalyst, the component (a) as a transition metal atom is about 5 × per 1 g of the carrier (c).
10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2
The aluminum atom (Al) derived from the component (b) and the component (d), which is supported in an amount of × 10 ⁻⁴ gram atom, has a molar ratio (Al / A) to the transition metal atom (M) derived from the component (a). M), 5-200, preferably 10-150
It is desirable that the particles are supported in an amount in the range.

Preliminary polymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Intrinsic viscosity [η] measured in decalin of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

The ethylene / α-olefin copolymers [A] and [B] used in the present invention are ethylene and an α-olefin having 3 to 20 carbon atoms, for example, in the presence of the above catalyst. Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1
It can be obtained by copolymerizing -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

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

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

When carrying out the slurry polymerization method or the gas phase polymerization method, the catalyst as described above is usually used as the concentration of the transition metal atom in the polymerization reaction system in the range of 10 ⁻⁸ to 10 ⁻³ gram atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In the main polymerization, the same organoaluminumoxy compound and / or organoaluminum compound (d) as the component (b) may be added. At this time, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10-20
The range is 0, more preferably 15 to 150.

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

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

When the ethylene / α-olefin copolymer [A] used in the present invention is produced by the slurry polymerization method, the polymerization temperature is usually -50 to 90 ° C, preferably 0.
When produced by a gas phase polymerization method in the range of -80 ° C,
It can be obtained by copolymerization under the condition that the polymerization temperature is usually 0 to 90 ° C, preferably 20 to 80 ° C.

When the ethylene / α-olefin copolymer [B] used in the present invention is produced by a slurry polymerization method, the polymerization temperature is usually in the range of -30 to 100 ° C, preferably 20 to 90 ° C. When producing by a gas phase polymerization method, the polymerization temperature is usually 20 to 120 ° C., preferably 40 to 120 ° C.
It can be obtained by copolymerization under the conditions of 100 ° C.

[Ethylene / α-olefin copolymer composition [I]] The ethylene / α-olefin copolymer composition comprises the ethylene / α-olefin copolymer [A] and
Consisting of ethylene / α-olefin copolymer [B],
The ethylene / α-olefin copolymer [A] is contained in an amount of 5 to 95% by weight, preferably 10 to 90% by weight, and the ethylene / α-olefin copolymer [B] is 5 to 95% by weight, preferably Is preferably contained in an amount of 10 to 90% by weight.

Ethylene / α-olefin copolymer [A]
And ethylene / α-olefin copolymer [B] are the ratio of the density of ethylene / α-olefin copolymer [A] to the density of ethylene / α-olefin copolymer [B] ([A] / [B]) is less than 1, preferably 0.930-
Used in combination so as to be 0.999. The ratio of the ethylene · alpha-olefin copolymer and the intrinsic viscosity [eta _A] of [A], and the intrinsic viscosity [eta _B] of the ethylene · alpha-olefin copolymer _{[B] ([η A]} / [Η _B ])
Is 1 or more, preferably 1.05 to 10, more preferably 1.1 to 5 in combination.

Such an ethylene / α-olefin copolymer composition has a density of 0.890 to 0.955 g / c.
m ³ is preferably in the range of 0.905 to 0.950 g / cm ³ , and the MFR is in the range of 0.1 to 100 g / 10 minutes, preferably 0.2 to 50 g / 10 minutes.

The ethylene / α-olefin copolymer composition can be produced by a known method, for example, the following method. (1) The ethylene / α-olefin copolymer [A], the ethylene / α-olefin copolymer [B], and other components optionally added are mechanically blended using an extruder, a kneader, or the like. how to.

(2) an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B],
And optionally other ingredients added to a suitable good solvent (eg; hexane, heptane, decane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene and xylene)
The method of dissolving in, and then removing the solvent.

(3) Ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer [B],
And a method in which other components optionally added are separately dissolved in a suitable good solvent, and then mixed, and then the solvent is removed.

(4) A method in which the above methods (1) to (3) are combined. Furthermore, the ethylene / α-olefin copolymer composition of the present invention can be used for copolymerization under different reaction conditions.
Ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer [B]
It can be produced by copolymerization of ethylene, α-
It can also be produced by copolymerizing the olefin copolymer [A] and the ethylene / α-olefin copolymer [B].

[High Pressure Radical Method Low Density Polyethylene [I
I]] Next, the high-pressure radical method low-density polyethylene used in the present invention will be specifically described.

High-pressure radical method low-density polyethylene is polyethylene with many branches having long-chain branches produced by so-called high-pressure radical polymerization. ASTM D1238-
MFR measured under 65T at 190 ° C. under a load of 2.16 kg is 0.1 to 50 g / 10 minutes, preferably 0.2
-10g / 10min, more preferably 0.2-8g / 1
It is desirable that the range is 0 minutes.

The high-pressure radical method low-density polyethylene according to the present invention has a molecular weight distribution index (Mw) measured by gel permeation chromatography (GPC).
/ Mn; where Mw: weight average molecular weight, Mn: number average molecular weight) and melt flow rate (MFR) are Mw / Mn ≧ 7.5 × log (MFR) −1.2, preferably Mw / Mn ≧ 7.5 × log (MFR)-
More preferably, it satisfies the relationship represented by Mw / Mn ≧ 7.5 × log (MFR).

The molecular weight distribution (Mw / Mn) of the high-pressure low-density polyethylene was measured as follows using GPC-150C manufactured by Millipore. Separation column is TS
K GNH HT, column size is 72m diameter
m, length 600 mm, column temperature 140 ° C., mobile phase using o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (Takeda Yakuhin) 0.025 wt% as an antioxidant, 1.0 ml The sample concentration is 0.
The sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <1000 and Mw> 4 × 10 ^6.
Is manufactured by Tosoh Corporation, and 1000 <Mw <4 × 1
As for 0 ⁶ , a product manufactured by Pressure Chemical Co. was used.

The high-pressure radical method low-density polyethylene according to the present invention has a density (d) of 0.910 to 0.930 g.
It is preferably in the range of / cm ³ . Density is 190
Strands obtained during melt flow rate (MFR) measurement at 2.16 kg load at 120 ° C
After heat treatment for 1 hour and cooling to room temperature over 1 hour, measurement is performed with a density gradient tube.

Further, the high-pressure radical method low-density polyethylene according to the present invention has a swell ratio representing the degree of long-chain branching,
That is, using a capillary flow characteristic tester, the diameter (D) of a strand extruded at a extrusion rate of 10 mm / min from a nozzle having an inner diameter (D) of 2.0 mm and a length of 15 mm under conditions of 190 ° C
It is desirable that the ratio (Ds / D) between the s) and the nozzle inner diameter D is 1.3 or more.

The high-pressure radical method low density polyethylene used in the present invention may be combined with other polymerizable monomers such as α-olefin, vinyl acetate and acrylate as long as the object of the present invention is not impaired. It may be a copolymer of

[Ethylene Copolymer Composition] The ethylene copolymer composition of the present invention comprises the ethylene / α-olefin copolymer composition [I], a high pressure radical method low density polyethylene [II], And the weight ratio ([I]: [II]) of the ethylene / α-olefin copolymer composition [I] and the high-pressure radical method low-density polyethylene [II] is 99:
It is preferably in the range of 1 to 60:40, more preferably in the range of 98: 2 to 70:30, and particularly preferably in the range of 98: 2 to 80:20.

If the amount of the high-pressure radical method low-density polyethylene is less than the above range, the modifying effects such as transparency and melt tension may be insufficient. If the amount is more than the above range, the tensile strength and the stress crack resistance may be poor. Etc. may decrease significantly.

Such an ethylene copolymer composition is
It can be produced using a known method, for example, the following method. (1) A method of mechanically blending an ethylene / α-olefin copolymer composition, a high-pressure radical method low-density polyethylene, and optionally other components, using an extruder, a kneader, or the like.

(2) The ethylene / α-olefin copolymer composition, the high-pressure radical method low-density polyethylene, and optionally other components added are mixed with a suitable good solvent (for example;
A solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then removing the solvent.

(3) Ethylene / α-olefin copolymer composition, high-pressure radical method low-density polyethylene, and other components optionally added are separately dissolved in a suitable good solvent to prepare a solution, which is then mixed. And then removing the solvent.

(4) A method in which the above methods (1) to (3) are combined. The ethylene-based copolymer composition of the present invention, within the range not impairing the object of the present invention, a weather resistance stabilizer,
Additives such as heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antiaging agents, hydrochloric acid absorbents, and antioxidants are required. It may be blended accordingly.

The ethylene copolymer composition of the present invention is processed into a film by ordinary air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooling inflation molding and the like. Obtainable. The film thus formed is excellent in transparency, mechanical strength and blocking resistance, and has the heat sealability, hot tack property, heat resistance and the like which are the features of ordinary LLDPE.
In addition, an ethylene / α-olefin copolymer [A],
Since the composition distribution of [B] is extremely narrow, the film surface is not sticky. Furthermore, since the stress is low even in the high shear region, high-speed extrusion is possible, power consumption is reduced, and it is economically advantageous.

The film obtained by processing the ethylene-based copolymer composition of the present invention is a standard bag, heavy bag, wrap film, raw lami film, sugar bag, oil packaging bag, aquatic packaging bag, food product. It is suitable for various packaging films for packaging, infusion bags, agricultural materials and the like. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester. Furthermore, it can also be used for blow infusion bags, blow bottles, extrusion-molded tubes, pipes, tear-off caps, injection-molded products such as daily sundries, fibers, and large-sized molded products by rotational molding.

[0128]

The ethylene-based copolymer composition of the present invention is
An ethylene / α-olefin copolymer composition comprising ethylene / α-olefin copolymers [A] and [B] having specific physical properties and different densities and MFRs, and a high pressure radical method low density polyethylene Since it is blended, a film having excellent heat stability and moldability, transparency, and blocking resistance can be produced.

[0129]

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

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

[Film Impact] The film impact was measured by a pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisakusho.

[Blocking Power] An inflation film cut into a size of 7 (width) × 20 cm is sandwiched between type papers and sandwiched between glass plates, and a load of 10 kg is applied in an air bath at 50 ° C. for 24 hours. The film was attached to an open jig at a rate of 200 mm / min, the load at this time was set to Ag, and the blocking force F (g / cm) was expressed as F = A / width of test piece. The smaller the value of F, the more difficult the blocking is, that is, the better the blocking resistance is.

[0133]

[Production Example 1] Production of ethylene / α-olefin copolymer [A-1] [Preparation of catalyst component] 7.9 kg of silica dried at 250 ° C for 10 hours was suspended in 121 liters of toluene. Cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 1.47 mol / liter)
41 liters were dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then washed with toluene 125
Resuspend in liter. To this system, a solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride in toluene (Zr = 28.4 mmol / liter) 20
Add liters at 30 ° C over 30 minutes, then add 30 ° C.
And reacted for 2 hours. Then, the supernatant was removed and the solid was washed twice with hexane to obtain a solid catalyst containing 4.6 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst] To 160 liters of hexane containing 16 mol of triisobutylaluminum, 4.3 kg of the solid catalyst obtained above was added,
Prepolymerization of ethylene was carried out at 35 ° C. for 3.5 hours to obtain a prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst. [Η] of this ethylene polymer
Was 1.27 dl / g.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 18 kg / cm ² -G and a polymerization temperature of 75 ° C. The prepolymerized catalyst prepared in the above [Preparation of prepolymerized catalyst] was continuously supplied at a rate of 0.05 mmol / h in terms of zirconium atom and 10 mmol / h of triisobutylaluminum to maintain a constant gas composition during the polymerization. In order to achieve this, ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.041, hydrogen / ethylene = 0.0
011 and ethylene concentration = 10%).

The yield of the ethylene / α-olefin copolymer (A-1) thus obtained was 6.0 kg / h, the density was 0.906 g / cm ³ , and the MFR was 0.32 g / 10.
The temperature at the maximum peak position of the endothermic curve measured by DSC is 92.5 ° C., the melt tension at 190 ° C. is 6.2 g, and the fluidity index is 89 (1
/ Sec), the decane-soluble portion at room temperature was 0.52% by weight, the number of unsaturated bonds was 0.090 per 1000 carbon atoms, and 0.90 per polymer molecule. .

[0137]

Example 1 [Preparation of ethylene / α-olefin copolymer composition] The ethylene / α-olefin copolymer (A-1) (density: 0.906 g / cm ³ ) obtained in Production Example 1 was used. The ethylene / α-olefin copolymer (B-1) (density: 0.949 g / cm ³ ) produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1 Melt kneading with a ratio (A-1 / B-1) of 57/43 to produce ethylene / α-
An olefin copolymer composition (L-1) was obtained.

Table 2 shows the physical properties of the ethylene / α-olefin copolymer composition (L-1) thus obtained. [Preparation of Ethylene Copolymer Composition] The ethylene / α-olefin copolymer composition (L-1) and the high pressure radical method low density polyethylene (H-1) shown in Table 3 are mixed at a mixing ratio (L- 1 / H-1) 90/10 by dry blending, and further to 100 parts by weight of resin, tri (2,2,2) as a secondary antioxidant
0.05 parts by weight of 4-di-t-butylphenyl) phosphate and n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate as a heat-resistant stabilizer were added. 0.
1 part by weight and 0.05 part by weight of calcium stearate as a hydrochloric acid absorbent were mixed. After that, a conical taper type twin-screw extruder manufactured by Haake Co. was used and kneaded at a set temperature of 180 ° C. to obtain an ethylene copolymer composition.

[Film Processing] Using the obtained ethylene-based copolymer composition, using a single screw extruder of 20 mmφ · L / D = 26, a 25 mmφ die, a lip width of 0.7 mm, and a single slit air ring, Air flow rate = 90 liters /
A film having a thickness of 30 μm was inflation-molded under the following conditions: min, extrusion rate = 9 g / min, blow ratio = 1.8, take-up speed = 2.4 m / min, processing temperature = 200 ° C.

The melt properties and film properties of the ethylene copolymer composition are shown in Table 4.

[0141]

Reference Example 1 [Film Processing] A film having a thickness of 30 μm was formed in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-1) produced in Example 1 was used. .

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-1). From Example 1 and Reference Example 1, it can be seen that the blending of the high-pressure radical method low-density polyethylene improved the melt tension and improved the transparency of the obtained film.

[0143]

Example 2 [Preparation of Ethylene / α-Olefin Copolymer Composition]
Production example except that the monomer content was adjusted as shown in Table 1.
Ethylene / α-olefin copolymer weight produced in the same manner as in No. 1
Combined (A-2) (Density: 0.916 g / cm³) And Eti
Ren / α-olefin copolymer (B-2) (density: 0.9
31 g / cm ³) At a weight ratio (A-2 / B-2) of 70/30
Melt-kneading and ethylene / α-olefin copolymer composition
(L-2) was obtained. Ethylene / α-olefin copolymer
Table 2 shows the physical properties of the composition (L-2).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-2) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, in the same manner as in Example 1 and having a thickness of 30 μm.
Was formed into a film.

The melt properties and film properties of the ethylene copolymer composition are shown in Table 4.

[0147]

Reference Example 2 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-2) produced in Example 2, Example 1 was used.
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-2). From Example 1 and Reference Example 1, it can be seen that the blending of the high-pressure radical method low-density polyethylene improved the melt tension and improved the transparency of the obtained film.

[0149]

Example 3 [Preparation of Ethylene / α-Olefin Copolymer Composition]
Production example except that the monomer content was adjusted as shown in Table 1.
Ethylene / α-olefin copolymer weight produced in the same manner as in No. 1
Combined (A-3) (Density: 0.907 g / cm³) And Eti
Ren / α-olefin copolymer (B-3) (density: 0.9
43 g / cm ³) At a weight ratio (A-3 / B-3) of 60/40
Melt-kneading and ethylene / α-olefin copolymer composition
(L-3) was obtained. Ethylene / α-olefin copolymer
Table 2 shows the physical properties of the composition (L-3).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-3) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, in the same manner as in Example 1, the thickness was 30 μm.
Was formed into a film.

Table 4 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0153]

Reference Example 3 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-3) produced in Example 3, Example 1 was used.
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-3). From Example 1 and Reference Example 1, it can be seen that blending high-pressure radical method low-density polyethylene improves transparency and melt tension.

[0155]

Comparative Example 1 [Preparation of Ethylene / α-Olefin Copolymer Composition] In Production Example 1, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was used instead of JP-B-63-5.
Ethylene produced in the same manner as in Production Example 1 except that the titanium-based catalyst component described in Japanese Patent No. 4289 was used, triethylaluminum was used instead of methylaluminoxane, and the comonomer content was adjusted as shown in Table 1. α-Olefin Copolymer (A-5) (Density: 0.915 g / cm ³ )
And ethylene / α-olefin copolymer (B-5) (density: 0.933 g / cm ³ ) in a weight ratio (A-5 / B-5) of 60
Melt kneading at 40/40 to obtain an ethylene / α-olefin copolymer composition (L-5). Table 2 shows the physical properties of the ethylene / α-olefin copolymer composition (L-5).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-5) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, in the same manner as in Example 1, the thickness was 30 μm.
Was formed into a film.

Table 4 shows melt properties and film properties of the ethylene copolymer composition. The obtained ethylene-based copolymer composition had a small melt tension as compared with Example 3 using the ethylene / α-olefin copolymer composition (L-3) having the same MFR and density. The film has poor film impact and blocking resistance.

[0159]

Comparative Example 2 [Preparation of Ethylene Copolymer Composition] An ethylene / α-olefin copolymer (C-1) produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1. )
An ethylene-based copolymer composition was obtained in the same manner as in Example 1 except that was used.

[Film Processing] Using the obtained ethylene-based copolymer composition, a thickness of 30 μm was obtained in the same manner as in Example 1.
Was formed into a film.

Table 4 shows the melt properties and film properties of the ethylene copolymer composition. The obtained ethylene-based copolymer composition had a fluidity in a high shear region as compared with Example 1 using the ethylene / α-olefin copolymer composition (L-1) having the same MFR and density. Is low, and the resulting film is inferior in film impact and blocking resistance.

[0162]

Example 4 Preparation of Ethylene / α-Olefin Copolymer Composition
Production example except that the monomer content was adjusted as shown in Table 1.
Ethylene / α-olefin copolymerized in the same manner as in No. 1
Polymer (A-4) (density; 0.916 g / cm ³) And made
In Production Example 1, bis (1,3-dimethylcyclopenta
Instead of dienyl) zirconium dichloride, bis (1-
Methyl-3-n-butylcyclopentadienyl) zirco
The comonomer content is listed in Table 1 using the aluminum dichloride.
Polymerization was carried out in the same manner as in Preparation 1, except that
In addition, ethylene / α-olefin copolymer (B-4)
Degree; 0.924 g / cm³), The weight ratio (A-4 / B-
4) Melt kneading at 20/80 and ethylene copolymer composition
The thing (L-4) was obtained. Ethylene / α-olefin copolymerization
Table 2 shows the physical properties of the body composition (L-4).

[Preparation of ethylene / α-olefin copolymer composition] An ethylene copolymer was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-4) was used. A composition was obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, a thickness of 30 μm was obtained in the same manner as in Example 1.
Was formed into a film.

Table 4 shows the melt properties and film properties of the ethylene copolymer composition.

[0166]

Reference Example 4 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-4) produced in Example 4, Example 1 was used.
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows melt properties and film properties of the ethylene / α-olefin copolymer composition (L-4). From Example 4 and Reference Example 4, it is understood that the blending of the high pressure radical method low density polyethylene improves the melt tension.

[0168]

[Table 1]

[0169]

[Table 2]

[0170]

[Table 3]

[0171]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Tsutsui 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

[Claims] 1. A copolymer of [I] (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-ii) density (d) is 0.880 to 0.8. 940 g / cm ³
(A-iii) the limiting viscosity [η _A ] measured in decalin at 135 ° C. in the range of 1.0 to 10.0 dl / g, and (A-iv) the differential scanning calorimeter (A-iv). The temperature (Tm (° C.)) at the maximum peak position of the endothermic curve measured by DSC and the density (d) satisfy the relationship represented by Tm <400 × d-250, and (A-v) melt tension at 190 ° C. (MT (g)) and melt flow rate (MFR) satisfy the relationship ^represented by MT> 2.2 × MFR ^−0.84 , and (A-vi) the stress at 190 ° C. of the molten polymer is 2.4 ×
The fluidity index (FI (1 / sec)) defined by the shear rate when reaching 10 ⁶ dyne / cm ² and the melt flow rate (MFR) satisfy the relationship represented by FI> 75 × MFR, A-vii) Decane-soluble part at room temperature (W (% by weight))
And the density (d) satisfy the relationship represented by W <80 × exp (−100 (d−0.88)) + 0.1, 5 to 95% by weight of an ethylene / α-olefin copolymer [A], (B-i) a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, (B-ii) having a density (d) of 0.910 to 0.960 g / cm ³
(B-iii) the limiting viscosity [η _B ] measured in decalin at 135 ° C. in the range of 0.5 to 2.0 dl / g, and (B-iv) the differential scanning calorimeter ( The temperature (Tm (° C.)) and the density (d) at the maximum peak position of the endothermic curve measured by DSC satisfy the relationship represented by Tm <400 × d-250, and (B-v) decane-soluble at room temperature When the part (W (% by weight)) and the density (d) are MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 min Then, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
0.88)) + 0.1, wherein the ethylene / α-olefin copolymer composition [B] is 5 to 95% by weight, and the ethylene / α-olefin copolymer composition comprises (i) The ratio ([A] / [B]) between the density of the ethylene / α-olefin copolymer [A] and the density of the ethylene / α-olefin copolymer [B] is less than 1, ) The ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] is 1 or more. And (iii) the density of the composition is in the range of 0.890 to 0.955 g / cm ³ , and (iV) the melt flow rate (MFR) of the composition at 190 ° C. and a load of 2.16 kg is 0. .1-10
An ethylene / α-olefin copolymer composition having a range of 0 g / 10 minutes, and [II] a low density polyethylene by a high pressure radical method, wherein (i) the melt flow rate (MFR) is 0.1 to 5
Within the range of 0 g / 10 minutes, (ii) the molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MF) measured by GPC.
R) and high-pressure radical method low-density polyethylene satisfying the relationship represented by Mw / Mn ≧ 7.5 × log (MFR) -1.2, and the above ethylene / α-olefin copolymer composition [I]
And a high-pressure radical method low-density polyethylene [II] in a weight ratio ([I]: [II]) within the range of 99: 1 to 60:40, the ethylene-based copolymer composition. .