JPH08283477A - Ethylenic copolymer composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition capable of providing a film excellent in thermal stability, moldability, transparency, mechanical strength and blocking strength by including two kinds of ethylene-α-olefin copolymers different in density and melt flow rate and having specific physical properties. CONSTITUTION: This composition contains (A) 5-95wt.% of an ethylene-α-olefin copolymer comprising a copolymer of ethylene with 3-20C α olefin, having (i) 0.880-0.940g/cm<3> density (d), (ii) 1.0-10.0dl/g intrinsic viscosity [η] in decalin at 35 deg.C, (iii) a temperature [Tm( deg.C)] and density at maximum peak position of endothermic curve of DSC which satisfy relationship of formula I and (iv) decalin-soluble part [W(wt.%)] and density at ambient temperature which satisfy formula II and (B) 5-95wt.% of an ethylene-α-olefin having (v) 0.910-0.975g/cm<3> density and (vi) 0.5-2.0dl/g intrinsic viscosity [η] and satisfying (vii) the relationship of formula III and having <1 density ratio A/B and >=1 [ηA]/[ηB].

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 excellent in transparency, mechanical strength 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.

On the other hand, it is known that an ethylene polymer obtained by using a metallocene catalyst system has a narrow composition distribution and a molded product such as a film has little stickiness. However, for example, JP-A-60-3500
In JP-A-7, there is a description 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. It is expected that the thermal stability will be poor like the ethylene polymer obtained by the above. 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.

The present inventors have conducted olefin polymerization containing (a) a compound of a transition metal of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton, and (b) an organoaluminumoxy compound. The ethylene / α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for use has excellent melt tension and thermal stability, and has a narrow composition distribution. I found that. However, such an ethylene / α-olefin copolymer is
Since the balance between melt tension and fluidity is not always good,
Problems could occur when extruded into a film. Therefore, as a result of further research, an ethylene / α-olefin copolymer obtained using the above catalyst and a catalyst system different from the above catalyst system were produced.
The ethylene / α-olefin copolymer is density, MF
An ethylene-based copolymer composition obtained by blending an ethylene-α-olefin copolymer composition obtained by blending ethylene / α-olefin copolymers different in R with a low-density polyethylene by a high-pressure radical method The present invention was found to be excellent in heat stability, melt tension and fluidity (FI) in a high shear region, and the obtained film is excellent in transparency, mechanical strength and blocking resistance, and thus completed the present invention. Came to do.

[0008]

OBJECT OF THE INVENTION It is an object of the present invention to provide a copolymer composition capable of producing a film which is excellent in heat stability and moldability and is excellent in transparency, mechanical strength and blocking resistance. I am trying.

[0009]

SUMMARY OF THE INVENTION A first ethylene / α-olefin copolymer composition according to the present invention is a copolymer of (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms, (A
-ii) The density (d) is in the range of 0.880 to 0.940 g / cm ³ , and (A-iii) the intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is 1.0 to 10.0 dl. (A-iv) temperature at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) (Tm (° C))
And the density (d) satisfy the relationship represented by Tm <400 × d−250, and (Av) the decane-soluble part (W (wt%)) at room temperature and the density (d) are W <80 × 5 to 95% by weight of an ethylene / α-olefin copolymer [A] satisfying the relationship represented by exp (−100 (d−0.88)) + 0.1, (Bi) ethylene, and a carbon number of 3 A copolymer of 20 to α-olefins,
(B-ii) Density (d) is 0.910 to 0.975 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 an ethylene / α-olefin copolymer composition comprising ethylene-α-olefin copolymer [B] of 5 to 95% by weight and a density (d) satisfying a relationship of Tm> 138 × d-6. And (i) the ratio of the density of the ethylene / α-olefin copolymer [A] to the density of the ethylene / α-olefin copolymer [B] ([A] / [B]) is 1 And (ii) the ratio of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] ([η _A ] / [η _B ]) is 1 or more, (iii) the density of the composition is in the range of 0.890 to 0.955 g / cm ³ , and (iv) the melt flow of the composition at 190 ° C. under a load of 2.16 kg. Rate (MFR) is 0.1-10
It is characterized by being in the range of 0 g / 10 minutes.

In a preferred embodiment of the present invention, the above ethylene / α-olefin copolymer composition [I] further comprises
Low density polyethylene [II] produced by the 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 ratio measured by GPC (Mw / Mn: Mw = weight average content d
Molecular weight, Mn = number average molecular weight) and melt flow rate (M
FR) means blending a high-pressure radical method low-density polyethylene that satisfies the relationship represented by Mw / Mn ≧ 7.5 × log (MFR) -1.2.

The above ethylene / α-olefin copolymer composition [I] and the above high pressure radical method low density polyethylene
A suitable weight ratio ([I]: [II]) with [II] is 99: 1 to
It is within the range of 60:40.

Such a copolymer composition can produce a film which is excellent in heat stability and moldability and is excellent in transparency, mechanical strength, blocking resistance and inflation moldability.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The copolymer composition according to the present invention will be specifically described below.

[Ethylene / α-olefin copolymer [A]] The ethylene / α-olefin copolymer [A] constituting the ethylene-based 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 obtained by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at the measurement temperature. 120
℃, measurement frequency 25.05MHz, spectrum width 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of.

The ethylene / α-olefin copolymer [A] has the following characteristics (A-ii) to (A-vi). (A-ii) Density (d) is 0.880
0.940 g / cm ³ , preferably 0.890 to 0.935
g / cm ³ , more preferably 0.900 to 0.930 g /
It is desirable to be in the range of cm ³ .

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

(A-vi) The n-decane soluble component amount fraction (W (wt%)) and the density (d) at room temperature are 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. Meets

The amount of soluble component of n-decane (the smaller the soluble component, the narrower the composition distribution) is about 3% 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) And the density (d) have the above relationship, the ethylene / α-olefin copolymer [A] used in the present invention has a narrow composition distribution.

Further, in the ethylene / α-olefin copolymer [A], the number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms, and 1 per polymer molecule. The following is desirable.

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 present in the presence of a (a) transition metal compound, (b) an organoaluminum oxy compound, (c) a carrier, and (d) an organoaluminum compound-containing polymerization catalyst, which will be described later. It can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms so that the density of the resulting copolymer will be 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 (B-vi). (B-ii) Density (d) is 0.910
0.975 g / cm ³ , preferably 0.915 to 0.96
0 g / cm ³ , more preferably 0.925 to 0.960
It is preferably in the range of 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. .6
It is preferably in the range of to 1.8 dl / g.

(B-iv) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.) and the density (d) preferably satisfy the relationship of Tm> 138 × d−6, preferably Tm> 128 × d + 4, and more preferably Tm> 110 × d + 21.

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. The following is desirable. Such an ethylene / α-olefin copolymer [B] can be produced by a conventionally known method.

Hereinafter, the ligand (a) having a cyclopentadienyl skeleton, which is a catalyst component suitable for copolymerization of the ethylene / α-olefin copolymer [A] constituting the copolymer composition of the present invention, will be described. A transition metal compound of Group iv of the Periodic Table of Elements,
The (b) organoaluminum oxy compound, (c) carrier, and (d) organoaluminum compound will be specifically described.

The transition metal compound (a) preferably used in the present invention (hereinafter sometimes referred to as "component (a)").
Is a compound of a transition metal of Group IVB of the periodic table having a bidentate ligand in which two groups selected from a specific indenyl group or a substituted product thereof are bonded via a lower alkylene group or a specific substituted cyclo group. There are transition metal compounds of Group IVB of the Periodic Table using a pentadienyl group as a ligand, and specifically, there are transition metal compounds represented by the following formula [I] or [II].

MKL ¹ _X-1 ... [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. 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 a divalent group such as a lower alkylene group. Is a bidentate ligand bonded via a divalent silicon-containing group such as a hydrocarbon group, a silylene group, and a substituted silylene group. Preferred examples of the substituted indenyl group here include at least a lower alkyl group such as a methyl group, an ethyl group, an iso-propyl group, and an n-propyl group, or a substituent including a halogen such as fluorine, chlorine, bromine, or iodine. It is an indenyl group containing one or more.

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, octoxy group and the like. 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) dimethylzirconium, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methyl. Zirconium monochloride, ethylene bis (indenyl) ethyl zirconium monochloride, ethylene bis (indenyl) methyl zirconium monobromide, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis {1- (4,5 , 6,7-Tetrahydroindenyl)} dimethylzirconium, ethylenebis {1- (4,5,6,7-tetrahydroindenyl)} methylzirconium monochloride, ethylenebis {1- (4,5,6,7) -Tetra Hydroindenyl)} zirconium dichloride, ethylene bis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dibromide, ethylene bis {1- (4-methylindenyl)} zirconium dichloride, ethylene bis { 1- (5-methylindenyl)} zirconium dichloride, ethylene bis {1- (6-
Methylindenyl)} zirconium dichloride, ethylenebis {1- (7-methylindenyl)} zirconium dichloride, ethylenebis {1- (5-methoxyindenyl)}
Zirconium dichloride, ethylenebis {1- (2,3-dimethylindenyl)} zirconium dichloride, ethylenebis {1- (4,7-dimethylindenyl)} zirconium dichloride, ethylenebis {1- (4,7-dimethoxy) Indenyl)} zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7
-Di-t-butylfluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (dimethylcyclopentadienyl) Examples thereof include phenyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, and diphenylsilylenebis (indenyl) zirconium dichloride. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including.
In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [I], ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride and diphenylsilylenebis (indenyl) zirconium dichloride are particularly preferable.

Another preferred embodiment of the transition metal compound (a) is a transition metal compound represented by the following formula [II]. 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 coordinated to the transition metal atom M. At least two ligands L
² is a substituted cyclopentadienyl group having at least one group selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or a hydrocarbon group having 3 to 10 carbon atoms. The ligand L ² other than the substituted cyclopentadienyl group has 1 to 1 carbon atoms.
2 is a hydrocarbon group, 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 M. )

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

L ² is a ligand that coordinates to a transition metal atom, and at least two of these ligands L ² are ligands having a cyclopentadienyl skeleton. The ligand having an enyl skeleton may have a substituent.

Specific examples of the ligand having a cyclopentadienyl skeleton include, for example, a cyclopentadienyl group,
Methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group Group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group, and other alkyl-substituted cyclopentadienyl groups or indenyl groups , 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like can be exemplified. These groups may be further substituted with a halogen atom, a trialkylsilyl group or the like.

Examples of the hydrocarbon group include alkylene groups such as ethylene and propylene, and substituted alkylene groups such as isopropylidene and diphenylmethylene. Examples of the transition metal compound represented by the general formula [II] include bis (cyclopentadienyl) zirconium dichloride,
Bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis ( n-hexylcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butyl Cyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride,
Bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-
Butylcyclopentadienyl) zirconium dimethyl,
Bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadiene) Enyl) zirconium hydride chloride, and the like. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [II], bis (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. The transition metal compound (a) used in the present invention may contain at least two transition metal compounds represented by the above general formula [II].

Ethylene / α-olefin copolymer (A)
In a preferred embodiment, at least one selected from the transition metal compounds represented by the general formula [I] is combined with at least one selected from the transition metal compounds represented by the general formula [II]. There is a mode used.

Specifically, a combination of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride and ethylenebis (indenyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclo) Pentadienyl) zirconium dichloride in combination with ethylene bis (indenyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride in combination with dimethylsilylene bis (indenyl) zirconium dichloride, bis (1-
Methyl-3-n-butylcyclopentadienyl) zirconium dichloride and diphenylsilylenebis (indenyl)
A combination with zirconium dichloride is preferred.

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, or may be a special compound. A benzene-insoluble organoaluminum oxy compound as disclosed in Kaihei 2-276807 may be used.

The aluminoxane as described above can be produced by a known method.

For example, there is a method in which an organoaluminum compound such as a trialkylaluminum is directly acted on with water, ice or steam in a medium such as benzene to recover it as a hydrocarbon solution.

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 trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisopropylaluminum; tricyclohexylaluminum, tricyclooctylaluminum and the like. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxide, etc. of Alkylaluminum alkoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminums and trialkylaluminums are particularly preferred. 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-mentioned organoaluminum compound is
Used alone or in combination. Examples of the solvent 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 and decane, cyclopentane and cyclohexane. , Cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorinated compounds, Hydrocarbon solvents such as bromides 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 dissolved in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 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) used in the present invention (hereinafter referred to as "compound")
It may be described as "minute (c)". ) Is an inorganic or
Organic compounds with a particle size of 10-300 μm, preferably
Or a solid of 20 to 200 μm in the form of granules or fine particles.
The body is used. Among them, the inorganic carrier is porous oxide
Preferred is SiO.₂, Al₂O₃, MgO
Etc. or mixtures thereof, eg SiO.₂-MgO, Si
O₂-Al₂O₃, SiO ₂-TiO₂, SiO₂-V₂O_Five, S
iO₂-Cr₂O₃, SiO₂-TiO₂-Examples of MgO, etc.
be able to. Among these SiO₂And Al₂O₃Or
At least one component selected from the group consisting of
Those that do are preferred.

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 ,
Alkali salts such as Al ₂ (SO ₄ ) ₃ , BaSO ₄ , Al (NO ₃ ) ₃ and Na ₂ O may be contained, and carbonates, sulfates, nitrates and oxides may be contained.

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 and a pore volume of 0.3 to 2. It is preferably 5 cm ² / g. The carrier is, if necessary, 100 to 1000 ° C., preferably 1
It is used by firing at 50 to 700 ° C.

Further, the carrier (c) which can be used in the present invention includes a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm. 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)") which is optionally used include 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.

Further, as an organoaluminum compound (d)
It is also possible to use a compound represented by the following general formula [IV]
Wear. R¹ _nAlY_3-n ... [IV] (in the formula [IV], R¹Is the same as above, and Y is -OR
²Group, -OSiR³ ₃Group, -OAlR^Four ₂Group, -NR^Five ₂Group,-
SiR⁶ ₃Group or -N (R⁷) AlR⁸ ₂And n is 1 to
2 and R², R³, R^FourAnd R⁸Is a methyl group, ethyl
Group, isopropyl group, isobutyl group, cyclohexyl
Group, phenyl group, etc., R^FiveIs a hydrogen atom, methyl
Group, ethyl group, isopropyl group, phenyl group, trimethyl
Such as a rusilyl group, R⁶And R⁷Is a methyl group,
For example, a chill group. ) Such organoaluminization
As the compound, specifically, the following compounds are used.
Can be (1) R¹ _nAl (OR²)_3-nA compound represented by, for example
Dimethyl aluminum methoxide, diethyl aluminum
Mutethoxide, diisobutylaluminum methoxide
(2) R¹ _nAl (OSiR³ ₃)_3-nA compound represented by
If Et₂Al (OSi Me₃), (Iso-Bu)₂Al (OSiM
e₃), (Iso-Bu)₂Al (OSiEt₃) Etc .; (3) R¹ _nAl (OAlR^Four ₂)_3-nCompounds represented by
If Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-B
u)₂Etc. (4) R¹ _nAl (NR^Five ₂)_3-nA compound represented by, for example
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt,
Et₂AlN (SiMe₃)₂, (Iso-Bu)₂AlN (SiMe₃)₂ 
Etc. (5) R¹ _nAl (SiR⁶ ₃)_3-nA compound represented by, for example
(Iso-Bu)₂AlSi Me₃ Etc .; (6) R¹ _nAl (N (R⁷) AlR⁸ ₂)_3-nCompound represented by
Thing, eg Et₂AlN (Me) AlEt₂, (Iso-Bu)₂AlN
(Et) Al (iso-Bu)₂ The above general formulas [III] and [IV]
Among the organoaluminum compounds represented by the general formula R
¹ ₃Al, R¹ _nAl (OR²)_3-n, R¹ _nAl (OAlR^Four ₂)_3-n
And a compound represented by
A group, in which n = 2, is preferred.

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

The contact of the above-mentioned components (a) to (d) can be carried out in an inert hydrocarbon solvent, and specifically, as an inert hydrocarbon medium used for preparing the catalyst,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride, chlorine Examples thereof include halogenated hydrocarbons such as benzene 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 ^-FourUsed in molar amounts, the concentration of component (a) is about 1
0^-Four~ 2 x 10^-2It is in the range of mol / liter. component
Source of aluminum of (b) and transition metal in component (a)
The child ratio (Al / transition metal) is usually 10 to 500.
Aluminum atom of component (d) used as necessary
(Al-d) and aluminum atom (Al-b) of component (b)
The atomic ratio (Al-d / Al-b) is usually in the range of 0.02 to 3.
is there. Component (a), component (b), component (c) and required
The mixing temperature for mixing and contacting the component (d) according to
Usually -50 to 150 ° C, contact time is 1 minute to 50 hours
Is.

Ethylene.α-obtained as described above
The catalyst used for producing the olefin copolymer [A] is
The transition metal atom derived from the component (a) is supported in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom per 1 g of the component (c),
Further, it is desirable that aluminum atoms derived from the component (b) and the component (d) are supported in an amount of 10 ^{−3 to} 5 × 10 ⁻² gram atom per 1 g of the component (c).

Ethylene / α-olefin copolymer [A]
The catalyst used for the production of the component (a) as described above,
Component (b), component (c) and optionally component (d)
It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above component (a), component (b), component (c) and, if necessary, component (d). You can

Examples of olefins used in the prepolymerization include α-olefins having 3 to 20 carbon atoms such as ethylene, propylene and 1-butene.
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
It is usually used in an amount of 10 ^{−6 to} 2 × 10 ⁻² mol / liter, and the component (a) is usually 5 × 10 ⁻⁶ per 1 g of the component (c).
Used in an amount of ˜5 × 10 ⁻⁴ mol. The atomic ratio of the aluminum of component (b) to the transition metal in component (a) (Al /
(Transition metal) is usually 10 to 500, preferably 20 to 2
00. The atomic ratio (Al-d / Al-b) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) which are used as necessary is usually 0.02.
The range is from 3 to 3. The prepolymerization temperature is −20 to 80 ° C., and the prepolymerization time is about 0.5 to 100 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
The amount is preferably 0.1 to 500 g per 1 g of the carrier (c). Further, in the prepolymerization catalyst, the component (a) as a transition metal atom is added in an amount of about 5 × 10 ^{−6 to} 5 × per 1 g of the carrier (c).
Aluminum atoms (Al) derived from the component (b) and the component (d), which are supported in an amount of 10 ⁻⁴ gram atom, have a molar ratio (Al / M) to the transition metal atom (M) derived from the component (a). ), It is desirable that the carrier be supported in an amount of 5 to 200.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
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 copolymer [A] used in the present invention can be prepared in the presence of the catalyst as described above.
Ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-
It is obtained by copolymerizing with methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the 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 the slurry polymerization include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane and decane; cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and the like. Alicyclic hydrocarbons;
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 carrying out the slurry polymerization method or the gas phase polymerization method, the above-mentioned catalyst usually has a concentration of transition metal atoms in the polymerization reaction system of usually 10 ^-8 to 10 ^-3 gram atom /
It is preferably used in liter volumes.

In the main polymerization, the same organoaluminumoxy compound and / or organoaluminum compound (d) as the component (b) may be added.

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

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

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

Next, the ethylene / α-olefin copolymer [B] constituting the copolymer composition of the present invention is, for example, the following [K] solid titanium catalyst component and [L] organometallic catalyst component. , [M] electron donor.

Such solid titanium catalyst component containing [K] magnesium, titanium, halogen and, if necessary, an electron donor (r), [L] organometallic catalyst component, and [M] electron donor. The olefin polymerization catalyst containing the body will be described.

The solid titanium catalyst component [K] used in the present invention is prepared by bringing the following magnesium compound, titanium compound and electron donor (r) into contact with each other.

Specific examples of the titanium compound used for preparing the solid titanium catalyst component [K] include, for example,
A tetravalent titanium compound represented by the following formula can be given. Ti (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦ 4) As such a compound, specifically, titanium tetrahalide such as TiCl ₄ or Ti (OCH) ₃ ) Cl ₃ , Ti
_{(O-iso-C 4 H} 9) trihalide, alkoxy titanium such as Br _3, Ti (OCH ₃₎ dihalogenated dialkoxy titanium, such as _{2 Cl 2, Ti (OCH 3} ) 3 monohalogenated trialkoxy such Cl Examples thereof include titanium and tetraalkoxytitanium such as Ti (OCH ₃ ) ₄ .

Of these, halogen-containing titanium compounds, preferably titanium tetrahalides, are preferred, and titanium tetrachloride is particularly preferred. In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [K] include a magnesium compound having a reducing ability such as dimethyl magnesium and a magnesium compound having no reducing ability such as magnesium chloride.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability may be a complex compound of the above magnesium compound and another metal, a complex compound or a mixture of another metal compound.

The solid titanium catalyst component [K] used in the present invention comprises the above-mentioned magnesium compound, the above-mentioned titanium compound and, if necessary, an electron donor.
It is formed by bringing (r) into contact.

Specific examples of the electron donor (r) used in the preparation of the solid titanium catalyst component [K] include the following compounds. Amines such as methylamine, ethylamine, dimethylamine, hexamethylenediamine, tributylamine and tribenzylamine; pyrroles such as pyrrole; pyrroline; pyrrolidine; indole; pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines Cyclic oxygen-containing compounds such as tetrahydrofuran; C1-C1 such as methanol, ethanol, propanol and isopropylbenzyl alcohol
18 alcohols; 6 to 6 carbon atoms which may have a lower alkyl group such as phenol, cresol and xylenol
Phenols of 20; ketones having 3 to 15 carbon atoms such as acetone and methyl ethyl ketone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde and propionaldehyde; methyl formate, methyl acetate, ethyl benzoate, propyl benzoate, benzoic acid 2 carbon atoms such as butyl, octyl benzoate, cyclohexyl benzoate and phenyl benzoate
To 30 organic acid esters; C2 to C15 acid halides such as acetyl chloride and benzoyl chloride; C2 to C20 ethers such as methyl ether, isopropyl ether and butyl ether; 2-isopentyl-2-
Diethers such as isopropyl-1,3-dimethoxypropane; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; acetonitrile, benzonitrile,
Nitriles such as tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride; metal acid esters such as butyl titanate and ethyl titanate are used.

When the above titanium compound, magnesium compound and electron donor (r) are brought into contact with each other, the following carrier compound is used to prepare a carrier-supported [K] solid titanium catalyst component. You can also

Examples of such a carrier compound include SiO ₂ and
Preferable examples include Al ₂ O ₃ , MgO, ZnO, ZnO ₂ , and styrene-divinylbenzene copolymer.
As a method for producing the solid titanium catalyst component [K],
Titanium compounds, magnesium compounds and electron donors
A known method for preparing a highly active titanium catalyst component from (r) can be adopted. The above components may be contacted in the presence of another compound containing silicon, phosphorus, aluminum, etc. as a reaction aid.

The method for producing the solid titanium catalyst component [K] will be briefly described below with some examples. (1) A method in which a solution containing a magnesium compound, an electron donor (r) and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, the titanium compound is contact-reacted. (2) A method in which a complex consisting of a magnesium compound and an electron donor (r) is reacted with an organometallic compound and then a titanium compound is subjected to a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method in which a titanium compound and an electron donor (r) are subjected to a catalytic reaction. At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound.

The amount of each of the above components used in preparing the solid titanium catalyst component [K] varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor (r) per mol of the magnesium compound is 0.01 to 10 moles,
It is preferably used in an amount of 0.05 to 5 mol, the titanium compound is 0.01 to 1000 mol, preferably 0.1 to 20 mol.
Used in an amount of 0 mol.

The solid titanium catalyst component [K] thus obtained contains magnesium, titanium, halogen and an electron donor (r) as essential components. In this solid titanium catalyst component [K], the halogen / titanium (atomic ratio) is about 2-200, preferably about 4-100, and the electron donor (r) / titanium (molar ratio) is about 0.1. 0
1 to 100, preferably about 0.05 to 50, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.

Next, the organometallic catalyst component [L] forming the olefin polymerization catalyst will be described. In the present invention, as the organometallic catalyst component [L], organometallic compounds of Group I to Group III metals of the periodic table are used, and specifically, the following compounds are used. (1) R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X may represent a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q = 3
Is an organoaluminum compound. _{^{(2) M 1 AlR 1 4}} ( wherein, M ¹ is Li, Na, a K, R ¹ is as defined above) alkylated complex of Group I metal and aluminum represented by. (3) R ¹ R ² M ² (wherein R ¹ and R ² are the same as above. M ² is M
g, Zn or Cd), a dialkyl compound of Group II or Group III.

Examples of the organoaluminum compound belonging to the above (1) include the following compounds. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above, m is preferably a number of 1.5 ≦ m ≦ 3), general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as described above, X is halogen, and m is preferably 0 <m <3), general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above) .M is preferably 2 ≦ m <3
R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is a halogen,
0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q =
3) can be mentioned.

When carrying out the solvent suspension polymerization, an inert hydrocarbon can be used as a polymerization solvent. Specific examples of such an inert hydrocarbon include propane,
Aliphatic hydrocarbons such as butane, decane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated carbonization such as ethylene chloride and chlorobenzene Examples thereof include hydrogen, and contact products thereof. Of these inert hydrocarbons, aliphatic hydrocarbons are particularly preferable.

In the polymerization system, the solid catalyst component [K] is usually used in an amount of about 0.0001 to 50 mmol, calculated as titanium atoms per liter of polymerization volume. The organometallic catalyst component [L] is used in an amount such that the metal atom contained in the organometallic catalyst component [L] is usually about 1 to 2000 mol per 1 mol of titanium atom in the polymerization system. . Further, the electron donor [M] is usually about 0. 3 per mol of the metal atom in the organometallic catalyst component [L].
It is used in an amount so as to be 001 to 10 mol. In addition, as the electron donor, the nitrogen-containing compound, the oxidation-containing compound, the phosphorus-containing compound, and the electron donor [E] described later can be used as necessary. The electron donor [E] is
0.1 per mol of metal atom in the organometallic catalyst component [L].
It is also possible to use it in such an amount that it will be 001 to 10 mol.

The polymerization temperature is usually about -50 to 200 ° C., and the pressure is usually set to atmospheric pressure to 100 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. The ethylene / α-olefin copolymer [B] used in the present invention has a polymerization temperature of usually -30 to 10 when produced by a slurry polymerization method.
In the case of producing by a gas phase polymerization method in the range of 0 ° C, the polymerization temperature is usually 20 to 120 ° C, preferably 40 to 100 ° C.
It can be obtained by copolymerizing under the condition of

[Ethylene / α-olefin Copolymer Composition] The ethylene / α-olefin copolymer composition comprises the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [A]. B] as a main constituent, and the ratio [A] / [B] [A] / [B] (% by weight)
Ratio) is in the range 5 to 95/95 to 5, preferably in the range 10 to 90/90 to 10.

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 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, preferably in the range of 0.900~0.950g / cm ^3, MFR is 0.1 to 100 g / 10 min, it is desirable that preferably in the range of 0.2 to 50 g / 10 min.

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) There may be mentioned a method in which the above methods (1) to (3) are combined.

[High Pressure Radical Method Low Density Polyethylene] 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, and is 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 / 10
It is desirable to be in the range of minutes.

The high-pressure radical method low-density polyethylene according to the present invention has an index (Mw) of molecular weight distribution measured by gel permeation chromatography (GPC).
/ Mn; where Mw: weight average molecular weight, Mn: number average molecular weight) and melt flow rate (MFR) are 7.5 × log (MFR) -1.2 ≦ Mw / Mn, preferably 7.5 × log (MFR) -0.5 ≦ Mw / Mn. More preferably, it satisfies the relationship expressed by 7.5 × log (MFR) ≦ Mw / Mn.

The molecular weight distribution (Mw / Mn) of the high-pressure low-density polyethylene is GPC-150C manufactured by Millipore.
Was measured as follows. Separation column is T
SK GNH HT, column size is 72m in diameter
m, length 600 mm, column temperature 140 ° C., mobile phase o-dichlorobenzene (Wako Pure Chemical Industries)
And BHT (Takeda) 0.025 as antioxidant
The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <1000 and Mw> 4 × 1
For 0 ⁶ , a product manufactured by Tosoh Corporation is used, and 1000 <Mw <4
For × 10 ⁶ , a pressure chemical 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 the condition 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] In a preferred embodiment of the present invention, the ethylene / α-olefin copolymer composition [A] and the ethylene / α-olefin copolymer composition [B] are used. The ethylene / α-olefin copolymer composition [I] consisting of is blended with low-density polyethylene [II] by the high pressure radical method.
-Weight ratio of the olefin copolymer composition [I] and the high pressure radical method low density polyethylene [II] ([I]: [I
I]) is preferably in the range of 99: 1 to 60:40, more preferably in the range of 98: 2 to 70:30, and more preferably in the range of 98: 2 to 80:20. .

When the amount of the high-pressure radical method low-density polyethylene is less than the above range, the effect of modifying transparency and melt tension may be insufficient, and when it is more than the above range, the tensile strength and the stress crack resistance may be poor. Etc. may decrease.

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 are added to 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 has a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, within a range that does not impair the object of the present invention. Additives such as pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, and antioxidants may be blended as necessary.

The ethylene-based 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 or the like. Obtainable. The film formed in this way has excellent mechanical strength and
It has heat sealing properties, hot tack properties, heat resistance, good blocking properties, etc., which are the characteristics of LDPE. Also,
Since the composition distribution of the ethylene / α-olefin copolymers [A] and [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. Further, it can 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.

[0129]

EFFECT OF THE INVENTION The copolymer composition of the present invention has ethylene / α-α having specific physical properties and different density and MFR.
The ethylene / α-olefin copolymer composition comprising the olefin copolymers [A] and [B], or the ethylene / α-olefin copolymer composition [I] comprising the above [A] and [B]. Since it is blended with the high-pressure radical method low-density polyethylene [II], a film having excellent thermal stability and moldability as well as excellent transparency, mechanical strength, and blocking resistance can be produced.

[0130]

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 ethylene copolymer composition and the film are evaluated as follows. [Flow index (FI)] It is defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² . The flow index (FI) is that the resin is extruded from the capillary while changing the shear rate.
It is determined by measuring the stress at that time. That is, using a sample similar to MT measurement, manufactured by Toyo Seiki Seisakusho,
It is measured with a capillary flow characteristic tester at a resin temperature of 190 ° C. and a shear stress range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

[Melt tension (MT (g))] Melt tension (M
T (g)) is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, the produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample. Using an MT measuring device manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C. and an extrusion speed of 15 mm
Min, winding speed 10-20m / min, nozzle diameter 2.09m
It was performed under the conditions of mφ and a nozzle length of 8 mm. At the time of pelletizing, the ethylene / α-olefin copolymer was preliminarily supplemented with 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and as a heat stabilizer. N-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.

The MFR of the resin to be measured (g / 10 minutes)
Change the diameter of the nozzle as follows and measure. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR [Haze] ASTM-D -1003-61.

[Dirt Impact] Measurement was performed according to the ASTM-D-1709 A method.

[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.
[Complete Heat Sealing Temperature (SIT)] It was measured by the following method. That is, with two sheets of film cut into a size of 120 × 120 mm stacked, a seal bar with a width of 5 mm kept at a temperature of 90 ° C. is pressed at a pressure of 2 kg / cm ² for one second on one side of the stacked films. The two films were heat-sealed to prepare test pieces. The heat sealer used was manufactured by Intesco. Next, cut out two pieces of film into a size of 15 × 15 mm including the heat seal part,
Peel off the parts other than the two heat-sealed parts, and place the opposite side that has been heat-sealed on the chuck of the tensile tester with a chuck distance of 1
It was set to 5 mm. The film was stretched at a tension rate of 300 mm / min until the film broke. When the seal portion was peeled off, the temperature of the seal bar was raised in steps of 5 ° C. and the above operation was repeated. The lowest temperature of the seal bar when the seal portion broke without peeling was defined as SIT.

[Tear strength] Using an Elmendorf tensile tester (manufactured by Toyo Seiki Seisakusho), in accordance with JIS Z1702,
The film take-up direction (MD) and the vertical direction (TD) are measured.

[0137]

[Production Example 1] Production of ethylene / α-olefin copolymer [A-1] [Preparation of catalyst component] 10.0 kg of silica dried at 250 ° C for 10 hours was suspended in 154 liters of toluene, Cooled to 0 ° C. Then, 57.5 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. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene. To this system, a solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride in toluene (Zr = 27.0 mm
ol / l) (16.8 l) was added dropwise at 80 ° C. over 30 minutes, and the reaction was continued at 80 ° C. for 2 hours. Then, the supernatant was removed and the solid was washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst] 870 g of the solid catalyst obtained above and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and ethylene preparatory was carried out at 35 ° C. for 5 hours. By carrying out the polymerization, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[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. 0.15 mmol of the prepolymerized catalyst prepared above in terms of zirconium atom
/ H, triisobutylaluminum 10 mmol / h
Of ethylene, 1-hexene, hydrogen and nitrogen in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
022, hydrogen / ethylene = 0.00006, ethylene concentration = 80%).

The obtained ethylene / α-olefin copolymer (A-1) had a yield of 5.8 kg / h, a density of 0.915 g / cm ³ , and an MFR of 0.53 g / 10.
The temperature at the maximum peak position of the endothermic curve measured by DSC is 106.8 ° C, the decane-soluble part at 23 ° C is 0.22% by weight, and the number of unsaturated bonds is 1000 carbon atoms. The number was 0.09 per molecule and 0.70 per molecule of the polymer.

The copolymer A-1 thus obtained is shown in Table 1.

[0142]

[Production Example 2] Production of ethylene / α-olefin copolymer [B-1] [Preparation of catalyst component] 1 mol of anhydrous magnesium chloride (commercially available product) was suspended in 2 liters of dehydrated and purified hexane under a nitrogen atmosphere. While stirring, 6 mol of ethanol was added dropwise over 1 hour, and the mixture was reacted at room temperature for 1 hour. After the reaction, 2.6 mol of diethylaluminum chloride was added dropwise thereto at room temperature, and stirring was continued for 2 hours. Next, after further adding 6 mol of titanium tetrachloride, the temperature of the system was raised to 80 ° C. and the reaction was carried out while stirring for 3 hours. After the reaction, the obtained solid was separated and washed repeatedly with purified hexane. This solid (α-
When the composition of 1) was examined, the composition was as follows.

[0143] TiClMgAlOEET ^*) (wt%) 3.6 66.8 20.0 0.4 4.7 ^{*) The} produced solid was decomposed and extracted with H ₂ O-acetone, and then quantified as ethanol by gas chromatography.

Next, in terms of Ti suspended in purified hexane,
To 50 mmol of α-1 was added 500 mmol of ethanol at room temperature, the temperature was raised to 50 ° C., and the reaction was carried out for 1.5 hours. After the reaction, the obtained solid part was repeatedly washed with purified hexane. The composition of the catalyst (β-1) thus obtained was as follows.

[0145] TiClMgAlOEET ^*) (wt%) 1.2 52.8 15.9 0.7 22.7

^{*) The} produced solid was decomposed and extracted with H ₂ O-acetone, and then quantified by gas chromatography as ethanol.

[Polymerization] Using a continuous reactor having an internal volume of 200 liters, dehydrated and purified hexane was added at 100 l / hr,
Diethylaluminum chloride 7 mmol / hr, ethylaluminum sesquichloride 14 mmol / hr and the catalyst (β-1) obtained above in terms of Ti of 0.
6 mmol / hr was continuously fed at such a ratio,
As raw material ethylene 13 kg / hr, 4-methyl-1-
Penten 19 kg / hr and hydrogen 45 l / hr were continuously fed into the polymerization vessel at a polymerization temperature of 165 ° C. and a total pressure of 30.
The copolymerization reaction was carried out under conditions of kg / cm ² G, average residence time of 1 hour, and a concentration of the copolymer in the solvent hexane of 130 g / l. The catalytic activity is 22100 g-copolymer /
It was mmol-Ti.

The copolymer thus obtained is shown in Table 2.

[0149]

Production Example 3 Production of Ethylene / α-Olefin Copolymer [B-2] Copolymer [B-2] according to the same production method as Production Example 2.
I got

The copolymer thus obtained is shown in Table 2. Further, an ethylene-1-butene copolymer (B-3) and an ethylene-propylene copolymer (B-4) produced by using a known solid titanium catalyst component, an organometallic component and a polymerization catalyst containing an electron donor. Was used.

Table 2 shows these copolymers.

[0152]

Example 1 [Preparation of Ethylene / α-Olefin Copolymer Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 (density: 0.915 g / cm ³ ). , Ethylene / α-olefin copolymer (B-1) (density: 0.945
g / cm ³ ) was melt-kneaded at a weight ratio (A-1 / B-1) of 60/40 to obtain an ethylene / α-olefin copolymer composition (L-1).

Table 3 shows the physical properties of the ethylene / α-olefin copolymer composition (L-1) thus obtained. [Preparation of ethylene-based copolymer composition] This ethylene / α
-Olefin copolymer composition (L-1) and high pressure radical method low density polyethylene (H-1) shown in Table 3 were dry blended at a mixing ratio (L-1 / H-1) of 85/15, Furthermore, tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to 0.05 parts by weight per 100 parts by weight of the resin.
Parts by weight, 0.1 parts by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate as a heat resistance stabilizer, and 0 parts by weight of calcium stearate as a hydrochloric acid absorbent. 0.05 parts by weight was compounded. Then, using a conical taper twin-screw extruder manufactured by Haake Co., set temperature 18
The mixture was kneaded at 0 ° C. to obtain an ethylene copolymer composition.

[Film Processing] Using the ethylene copolymer composition obtained, a single screw extruder of 50 mmφ · L / D = 26, a die of 150 mmφ, a lip width of 2.0 mm and a two-stage air ring were used. The air flow rate was adjusted so that the frost line was 20 cm, extrusion rate = 380 g / min, blow ratio = 1.8, take-up speed = 18 m / min, processing temperature =
A film having a thickness of 30 μm was inflation-molded under the condition of 200 ° C.

Melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6.

[0156]

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

The melt properties and film properties of the ethylene / α-olefin copolymer composition (L-1) are shown in Tables 5 and 6.

[0158]

Comparative Example 1 [Preparation of Ethylene / α-Olefin Copolymer Composition] In Production Example 1, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride was used instead of JP-B-63-54289. Same as Production Example 1, except that the titanium-based catalyst component described in Japanese Patent Publication No. JP-A-2003-13898 was used, triethylaluminum was used in place of methylaluminoxane, and the gas composition ratio was changed so that the comonomer content shown in Table 1 was obtained. The ethylene / α-olefin copolymer (A-5) (density: 0.915 g / cm ³ ) as shown in Table 1 and the ethylene / α-olefin copolymer (B −
1) (density: 0.945 g / cm ³ ) to the weight ratio (A-5 / B
-1) Melt kneading at 60/40 to obtain an ethylene / α-olefin copolymer composition (L-2). Table 3 shows the physical properties of the ethylene / α-olefin copolymer composition (L-2).

[Preparation of Ethylene Copolymer Composition] Using the ethylene / α-olefin copolymer composition (L-2), the high pressure radical method low density polyethylene (H
An ethylene-based copolymer composition was obtained in the same manner as in Example 1 except that the -1) and the -1) were mixed at a mixing ratio (L-2 / H-1) of 85/15.

[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.

The melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6. The film obtained has the same density and MFR as ethylene / α-
Example 1 using the olefin copolymer composition (L-1)
In comparison with the obtained film, the film impact,
It can be seen that the blocking force and tear strength are poor.

[0162]

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

The melt properties and film properties of the ethylene / α-olefin copolymer composition (L-2) are shown in Tables 5 and 6. From Comparative Example 1 and Comparative Example 2, as compared with Example 1, Comparative Example 1 shows that the obtained film has less improvement in transparency, high fluidity index (FI), poor blocking force and tear strength, Similarly to Example 2, Example 2 also has a high fluidity index (FI) and is inferior in blocking force and tear strength.

[0164]

Example 3 [Preparation of Ethylene / α-Olefin Copolymer Composition] An ethylene / α-olefin copolymer (manufactured in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1) a-1) (density; and 0.915g / cm ^3), ethylene · alpha-olefin copolymer prepared by the method of example 3 (B-2) (density; and 0.930g / cm ^3),
The mixture was melt-kneaded at a weight ratio (A-1 / B-2) of 60/40 to obtain an ethylene / α-olefin copolymer composition (L-3). Table 3 shows the physical properties of the ethylene / α-olefin copolymer 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.

The melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6.

[0168]

Embodiment 4

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 2 except that the ethylene / α-olefin copolymer composition (L-3) was used. 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.

The melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6.

[0172]

[Comparative Examples 3 and 4] [Preparation of ethylene / α-olefin copolymer composition] An ethylene / α-olefin copolymer produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1. polymer (a-5) (density; 0.915g / cm ³⁾ and the ethylene · alpha-olefin copolymer prepared by the method of example 3 (B-2) (density; 0.930g / cm ³⁾ and To
The mixture was melt-kneaded at a weight ratio (A-5 / B-2) of 60/40 to obtain an ethylene / α-olefin copolymer composition (L-4). Table 3 shows the physical properties of the ethylene / α-olefin copolymer composition (L-4).

[Preparation of Ethylene Copolymer Composition] The ethylene copolymer composition was the same as Example 1 or Example 2 except that the ethylene / α-olefin copolymer composition (L-4) was used. A polymer 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.

The melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6.

[0176]

[Comparative Examples 5 and 6] [Preparation of ethylene / α-olefin copolymer composition] An ethylene / α-olefin copolymer produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1. The combined product (C-1) (density: 0.922 g / cm ³ ) was used. The physical properties are shown in Table 1.

[Preparation of Ethylene Copolymer Composition] The ethylene copolymer composition was the same as in Example 1 or Example 2 except that the ethylene / α-olefin copolymer composition (C-1) was used. A polymer composition was 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 Tables 5 and 6.

[0180]

Examples 5 and 6 [Preparation of Ethylene / α-Olefin Copolymer Composition] The ethylene / α-olefin copolymer (A-1) produced in Production Example 1 (density: 0.915 g / cm ³ ). And ethylene / α-olefin copolymer (B-3) (density: 0.930
g / cm ³ ) was melt-kneaded at a weight ratio (A-1 / B-3) of 65/35 to obtain an ethylene / α-olefin copolymer composition (L-5). Table 3 shows the physical properties of the ethylene / α-olefin copolymer composition (L-5).

[Preparation of Ethylene Copolymer Composition] The ethylene copolymer composition was the same as in Example 1 or Example 2 except that the ethylene / α-olefin copolymer composition (L-5) was used. A polymer composition was 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 Tables 5 and 6.

[0184]

[Comparative Examples 7 and 8] [Preparation of ethylene / α-olefin copolymer composition] An ethylene / α-olefin copolymer produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 3. Polymer (A-5) (density: 0.915 g / cm ³ ) and the like, and ethylene / α-olefin copolymer (B-3) manufactured by the method of Production Example 3 (density: 0.947 g / cm ³ ). And were melt-kneaded at a weight ratio (A-5 / B-3) of 65/35 to obtain an ethylene / α-olefin copolymer composition (L-6). Ethylene / α-olefin copolymer composition (L-
Table 3 shows the physical properties of 6).

[Preparation of Ethylene Copolymer Composition] The ethylene copolymer composition was the same as in Example 1 or Example 2 except that the ethylene / α-olefin copolymer composition (L-6) was used. A polymer composition was 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 Tables 5 and 6. As shown in Tables 5 and 6, it can be seen that the film of Comparative Example 7 has a high flow index (FI) value and is inferior in dirt impact, blocking force and tear strength (MD, TD). Further, the film of Comparative Example 8 also has a high flow index (FI) value, and the blocking force and the tear strength (T
It turns out that it is inferior in D).

[0188]

[Examples 7 to 12] [Preparation of ethylene / α-olefin copolymer composition] Same as Production Example 1 except that the ethylene / α-olefin copolymer shown in Component A column of Table 3 was used for preparation. Ethylene-α-olefin copolymers (A-2) to (A
-4), and ethylene / α-olefin copolymers (B-3) and (B produced by the methods of Production Examples 2 to 3).
-4) or (B-1) are melt-kneaded at a mixing ratio shown in Table 3 to prepare an ethylene / α-olefin copolymer composition (L
-7) to (L-9) were obtained. Table 3 shows each physical property of the ethylene / α-olefin copolymer composition (L-7) to (L-9).
Shown in

[Preparation of ethylene-based copolymer composition] Instead of the ethylene / α-olefin copolymer composition (L-1), ethylene / α-represented by the code number I in Table 5 was used.
As shown in the column of code number II in Table 5, (H-1) was used except that the olefin copolymer compositions (L-7) to (L-9) were used and mixed at the mixing ratio shown in Table 5. Ethylene copolymer compositions were obtained in the same manner as in Example 1 or Example 2 with the mixing ratios shown in the mixing ratio column of Table 5.

[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.

The melt properties and film properties of the ethylene copolymer composition are shown in Tables 5 and 6.

[0192]

[Table 1]

[0193]

[Table 2]

[0194]

[Table 3]

[0195]

[Table 4]

[0196]

[Table 5]

[0197]

[Table 6]

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

Claims (4)

[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 0.8.
The range is 80 to 0.940 g / cm ³ , and (A-iii) 1
The intrinsic viscosity [η _A ] measured in decalin at 35 ° C. was 1.
It is in the range of 0 to 10.0 dl / g, and the temperature (Tm (° C)) and the density (d) at the maximum peak position of the endothermic curve measured by (A-iv) differential scanning calorimeter (DSC) are Tm. <400 × d−250, the decane-soluble part (W (wt%)) at room temperature (Av) and the density (d) are W <80 × exp (−100 (d-0) .88)) + 0.1 of an ethylene / α-olefin copolymer [A] satisfying the relationship shown by (B-i) ethylene and an α-olefin having 3 to 20 carbon atoms. A copolymer,
(B-ii) Density (d) is 0.910 to 0.975 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 an ethylene / α-olefin copolymer composition comprising ethylene-α-olefin copolymer [B] of 5 to 95% by weight and a density (d) satisfying a relationship of Tm> 138 × d-6. And (i) the ratio of the density of the ethylene / α-olefin copolymer [A] to the density of the ethylene / α-olefin copolymer [B] ([A] / [B]) is 1 And (ii) the ratio of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] ([η _A ] / [η _B ]) is 1 or more, and (iii)
The composition has a density in the range of 0.890 to 0.955 g / cm ³ and (iv) a melt flow rate (MFR) of 0.1 to 1 at 190 ° C. and a load of 2.16 kg.
An ethylene / α-olefin copolymer composition having a range of 00 g / 10 minutes. 2. [I] The ethylene.α- according to claim 1.
An olefin copolymer composition, 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 ratio (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, wherein the ethylene / α-olefin copolymer composition [I ]
And the high-pressure radical method low-density polyethylene [II] in a weight ratio ([I]: [II]) within the range of 99: 1 to 60:40, an ethylene-based copolymer composition. . 3. The copolymer composition according to claim 1, which is a film for inflation molding. 4. A film obtained by inflation molding using the copolymer composition according to claim 1 or 2.