JPH06136196A - Ethylene copolymer composition - Google Patents

Abstract

PURPOSE:To provide an ethylene copolymer compsn. improved in flowability in a high shear range, mechanical strength, transparency and blocking resistance, by using 2 kinds of specific ethylene-alpha-olefin copolymers. CONSTITUTION:(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 10dl/g, a Tm vs. d relationship: Tm<400Xd-250 [wherein Tm ( deg.C) is a temp. at the maximum peak in an endothermic curve measured with a differential scanning calorimeter], an MT vs. MFR relationship: MT<=2.2XMFR<-0.84> [wherein MT (g) is a melt tension at 190 deg.C, and MFR is a melt flow rate at 190 deg.C], etc., is blended with (B) 5-95wt.% ethylene-3-20C alpha-olefin copolymer with d=0.910 to 0.960g/cm<3>, zetaB=0.5 to 2dl/g, Tm<400Xd-250, etc., provided that the A/B density ratio is at most 1, zetaA/zetaB=1 or higher, d=0.890 to 0.955g/cm<3>, and MFR=0.1 to 100g/10min.

Description

Detailed Description of the Invention

[0001]

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

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 a small stress in the high shear region, a good thermal stability, an excellent mechanical strength, and a narrow composition distribution appears, its industrial value is extremely large. .

As a result of intensive studies in view of such circumstances, the present inventors have found that (a) a compound of a transition metal of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton, b) In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and a carbon number of 3 to 20
Ethylene obtained by copolymerizing with α-olefin
It was found that the α-olefin copolymer has excellent thermal stability and a narrow composition distribution. However, since such an ethylene / α-olefin copolymer does not always have good fluidity, problems may occur when it is extrusion-molded into a film.

Then, as a result of further research, an ethylene-based copolymer obtained by blending two kinds of ethylene / α-olefin copolymers having different densities and MFRs obtained by using the above catalyst The composition has excellent thermal stability and flowability (FI) in a high shear region, and
The obtained film was found to be excellent in transparency, mechanical strength and blocking resistance, and completed the present invention.

[0009]

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

[0010]

SUMMARY OF THE INVENTION The ethylene-based copolymer composition according to the present invention is a copolymer of (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms and has (A-ii) density. (D) is 0.
880 to 0.940 g / cm ³ , and (A-iii)
The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is in the range of 1.0 to 10 dl / g, and (A-iv) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC). The temperature (Tm (° C.)) and the density (d) satisfy the relationship represented by Tm <400 × d-250, and the melt tension (MT (g)) at 190 ° C. (A-v) and the melt flow rate ( MFR)
^Satisfy the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 , and (A-vi) the decane-soluble part (W (wt%)) and the density (d) at room temperature are W <80 × exp (−100 (d−0.88)) + 0.1 The ethylene / α-olefin copolymer [A] 5 to 95% by weight, the (Bi) ethylene, and the carbon number 3 to 3 are satisfied. A copolymer of 20 α-olefins,
(B-ii) Density (d) is 0.910 to 0.960 g / cm ^3.
And (B-iii) the intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is in the range of 0.5 to 2 dl / g, and (B-iv) differential scanning calorimeter (DSC). The temperature at the maximum peak position (Tm
(C)) and the density (d) satisfy the relationship represented by Tm <400 × d-250, and (B-v) the decane-soluble part (W (wt%)) and the density (d) at room temperature. But MFR ≦ 1
At 0 g / 10 minutes, W <80 * exp (-100 (d-0.88)) + 0.1 MFR> At 10 g / 10 minutes, W <80 * (MFR-9) ^0.26 * exp (-100 (D-
0.88)) + 0.1 which is an ethylene / α-olefin copolymer [B] is an ethylene-based copolymer composition comprising 5 to 95% by weight, wherein (i) the above-mentioned ethylene The ratio of the density of the α-olefin copolymer [A] to the density of the ethylene / α-olefin copolymer [B] ([A] / [B]) is less than 1, and (ii) the ethylene The ratio of the intrinsic viscosity of the 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)
It is characterized in that the melt flow rate (MFR) of the composition at 190 ° C. under a load of 2.16 kg is in the range of 0.1 to 100 g / 10 minutes.

Such an ethylene-based copolymer composition is
It is possible to produce a film having excellent thermal stability and fluidity (FI) in a high shear region, and having excellent mechanical strength and blocking resistance.

[0012]

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 comprises an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B].

[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.

The ethylene / α-olefin copolymer [A] has the following characteristics (A-ii) to (A-vi). (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 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 dl / g, preferably 1.25 to 8 dl / g, more preferably 1.27 to 6
It is preferably in the range of dl / g.

The melt flow rate (MFR) is
Measured according to ASTM D1238-65T under conditions of 190 ° C. and 2.16 kg load. (A-iv) The temperature (Tm (° C.)) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d-250, preferably Tm <450. Xd-297 More preferably, Tm <500 * d-344, particularly preferably Tm <550 * d-391.

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-v) The melt tension (MT (g)) and the melt flow rate (MFR) satisfy the relationship represented by ^MT≤2.2 × MFR- ^0.84 .

The melt tension (MT (g)) is determined by measuring the stress when the melted polymer is stretched at a constant rate. That is, the generated polymer powder is melted by a usual method and then pelletized to obtain a measurement sample,
Toyo Seiki Seisakusho's MT measuring instrument, resin temperature 190
C, extrusion speed 15 mm / min, winding speed 10-20
m / min, nozzle diameter 2.09 mmφ, nozzle length 8 mm. When pelletizing, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to the ethylene / α-olefin copolymer [A] beforehand, and it was heat resistant and stable. N-octadecyl-as an agent
0.1% by weight of 3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added.

(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−0.8)
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 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] according to 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 [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 quantification of unsaturated bonds was carried out 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-based copolymer composition of 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.

Such an ethylene / α-olefin copolymer [B] has the following characteristics (B-ii) to (B-vi). (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 dl / g, preferably 0.55 to 1.9, more preferably 0.6 to 1. .8d
It is preferably in the range of 1 / g.

(B-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.

(B-v) The n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at room temperature are MFR ≦ 10.
When g / 10 minutes, 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] according to 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 0.5 or less per 1000 carbon atoms, and 1 per polymer molecule. The following is desirable.

Ethylene / α-having the above characteristics
The olefin copolymer [B] is used for olefin polymerization, which is formed from (a) a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier, and (d) an organoaluminum compound, if necessary. In the presence of a catalyst, ethylene and an α-olefin having 3 to 20 carbon atoms,
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 .

Ethylene / α-olefin copolymers [A] and [B] constituting the ethylene-based copolymer composition of the present invention.
Is a transition metal compound of group IV of the periodic table containing (a ') a ligand having a cyclopentadienyl skeleton as described below, (b) an organoaluminum oxy compound, and (c)
By copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms under the conditions as described below in the presence of a carrier and, if necessary, a catalyst for olefin polymerization formed from (d) an organoaluminum compound. It can be manufactured.

The ethylene / α-olefin copolymer [A], which constitutes the ethylene copolymer composition of the present invention,
(A) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is used in the copolymerization of [B], and (a ′) a coordination having a cyclopentadienyl skeleton A transition metal compound of Group IV of the periodic table containing a child,
The (b) organoaluminum oxy compound, (c) carrier, and (d) organoaluminum compound will be specifically described.

The (a) transition metal compound (hereinafter sometimes referred to as "component (a)") used in the present invention is a transition metal compound represented by the following formula [I]. ML ¹ _x ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the periodic table, and L ¹ is a ligand that coordinates with the transition metal atom M. At least two ligands L ¹
Is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group or a carbon number of 3 to
A substituted cyclopentadienyl group having at least one substituent selected from the hydrocarbon groups of 10 (substituted)
The ligand L ¹ other than the cyclopentadienyl group has 1 carbon atom
~ 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
It is a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. In the above formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

L ¹ is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
A substituted cyclopentadienyl group having at least one substituent selected from an ethylcyclopentadienyl group or a hydrocarbon group having 3 to 10 carbon atoms, which is a ligand L other than a (substituted) cyclopentadienyl group. ¹ has 1 to 12 carbon atoms
Is a hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. The substituted cyclopentadienyl group has at least 1 when it has two or more substituents.
The number of the substituents may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents may be a methyl group, an ethyl group or a carbon number of 3 to 3
10 hydrocarbon groups. Further, the substituted cyclopentadienyl groups coordinated to M may be the same or different.

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

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

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

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

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. Are exemplified, and examples of the aryloxy group include a phenoxy group and the like.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include 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 bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (ethylcyclopentadienyl). Zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclo) Pentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium Bromide, bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclo) Pentadienyl) 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-butylcyclopentadienyl) zirconium hydride chloride,

And the like. In the above example, disubstituted cyclopentadienyl rings are 1,2- and 1,
3-substitutes are included, and tri-substitutes include 1,2,3- and 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 [I], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis ( 1-
Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are 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 [II] is preferable.

ML ² _x ... [II] [wherein M is a transition metal selected from Group IVB of the periodic table, L ² is a ligand that coordinates to the transition metal, and at least one L ² is a ligand having a cyclopentadienyl skeleton, and L ² 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. Base, SO ₃
R group (provided that 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 valence of the transition metal. ]

In the above general formula [II], M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, and 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 general formula [II] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons among them 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 ² other than the ligand having a cyclopentadienyl skeleton include the following. As the hydrocarbon group having 1 to 12 carbon atoms,
Examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Examples thereof include a cyclopentyl group and a cyclohexyl group, examples of the aryl group include a phenyl group and tolyl group, and examples of the aralkyl group include a benzyl group and a neophyll group.

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 [II ′] when the valence of the transition metal is 4.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [II '] (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 transition metal compounds in which M is zirconium will be 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 examples, 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.

It is also possible to use a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above.

As the compound (a ') used in the present invention, the above exemplified compounds can be used as a catalyst.
It is preferable to use the transition metal compound (a),
Among these, it is more desirable to use a compound that is particularly preferably used for the transition metal compound (a) as a catalyst. Further, it is particularly desirable to use a compound in which (a ′) and the transition metal compound of (a) are the same as a catalyst.

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 trialuminum.
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 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 organoaluminum compound as described above 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 dissolved in benzene at 60 ° C. is 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

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

The carrier (c) used in the present invention (hereinafter sometimes referred to as "component (c)") is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to. 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 above 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, 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)”) that is used as necessary include, for example, the organoaluminum compounds represented by the following general formula [II]. can do.

R ¹ _n AlX _3-n ... [II] (In the formula [II], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1
It is 3. In the above general formula [II], 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,
Examples thereof include n-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), a compound represented by the following general formula [III] can also be used. R ¹ _n AlY _3-n ... [III] (In the formula [III], 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 Among the organoaluminum compounds represented by the above general formulas [II] and [III], general formulas R ¹ ₃ Al and R ¹ _n Al (O
The compounds represented by R 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 (b), component (c) and, if necessary, a component. It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of (d). 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

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.

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 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 the 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 the 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-Based Copolymer Composition] The ethylene-based copolymer composition of the present invention comprises the ethylene / α-olefin copolymer [A] and the 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 included in an amount of 5 to 95% by weight. %, Preferably 10-90% by weight
It is desirable to be included in the amount of.

The ethylene / α-olefin copolymers [A] and [B] are the density of the ethylene / α-olefin copolymer [A] and the density of the ethylene / α-olefin copolymer [B]. Are used in combination so that the ratio ([A] / [B]) is less than 1, preferably 0.930 to 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
10 It is desirable to use them in combination so as to be more preferably 1.1 to 5.

Such an ethylene copolymer composition is
Density 0.890~0.955g / cm ^3, preferably in the range from 0.900~0.950g / cm ^3, MFR
Is 0.1 to 100 g / 10 minutes, preferably 0.2 to 50 g
The range of / 10 minutes is desirable.

The ethylene-based copolymer composition of the present invention comprises
Within the range that does not impair the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antiaging agent. Additives such as a hydrochloric acid absorbent and an antioxidant may be blended as necessary.

The ethylene-based copolymer composition of the present invention can be produced by a known method, for example, the following method. (1) The ethylene / α-olefin copolymer [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) an ethylene / α-olefin copolymer [A] and an 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-based copolymer composition of the present invention is divided into two or more stages under different reaction conditions for the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B]. ], And a plurality of polymerization vessels are used. In each of the polymerization vessels, ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer [B] are produced. It can also be produced by copolymerizing.

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 and 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 copolymer composition of the present invention is a standard bag, a heavy bag, a wrap film, a raw lami film, a sugar bag, an oil packaging bag, an aquatic packaging bag, a 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.

[0113]

The ethylene-based copolymer composition of the present invention is
Blended with ethylene / α-olefin copolymers [A] and [B], which have specific physical properties and different densities and MFRs, they have excellent thermal stability and moldability, mechanical strength, and blocking resistance. An excellent film can be manufactured.

[0114]

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)] Flow index (F
I) has a shear stress of 2.4 × 10 ⁶ dyn at 190 ° C.
It is defined as the shear rate when reaching e / 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 the 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
It is measured at about 3 × 10 ⁶ dyne / cm ² .

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 (Haze)] ASTM-D-1003-61
Was measured according to. [Film Impact] It 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, 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.

[0119]

[Production Example 1] Production of ethylene / α-olefin copolymer [A] [Preparation of catalyst] Silica 10 dried at 250 ° C for 10 hours
After suspending kg with 154 liters of toluene,
Cooled to ° C. Then, 57.5 liters of a toluene solution of methylaminooxane (Al = 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system is 0 ℃
Kept at. Continue to react for 30 minutes at 0 ° C, then 1.
It heated up to 95 degreeC over 5 hours, and was made to react 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. Bis (1-methyl-3-n-)
Toluene solution of butylcyclopentadienyl) zirconium dichloride (Zr = 27.0 mmol / liter)
16.8 liters of the mixture were put in a suitable temperature at 80 ° C. for 30 minutes, and further reacted at 80 ° C. for 2 hours. After that, the supernatant was removed and washed twice with hexane to obtain 3.
A solid catalyst containing 5 mg of zirconium was obtained.

[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 was preliminarily stored 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 were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
034, hydrogen / ethylene = 1.7 × 10 ⁻⁴ , ethylene concentration = 20%).

The yield of the obtained ethylene / α-olefin copolymer (A-1) was 5.8 kg / hr, the density was 0.908 g / cm ³ , and the melt flow rate (M
FR) is 0.77 g / 10 min, the temperature of the maximum peak position of the endothermic curve measured by DSC is 93.6 ° C, the decane-soluble part at room temperature is 0.51 parts by weight, and the unsaturated bond Was 0.08 per 1000 carbons and 0.70 per molecule of polymer.

[0123]

Example 1 [Preparation of Composition] Ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 (density: 0.908 g / c)
m ³ ) and the ethylene / α-olefin copolymer (B-1) (density: 0.938 g / c) produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1.
m ³ ) was melt-kneaded at a weight ratio (A-1 / B-1) of 60/40 to obtain an ethylene-based copolymer composition.

The density of the obtained ethylene copolymer composition was 0.921 g / cm ³ , and the MFR was 2.0 g / 10.
It was a minute. [Film processing] Using this ethylene-based copolymer composition, a single-screw extruder of 20 mmφ · L / D = 26, 25 mm
φ die, lip width 0.7mm, using single slit air ring, air flow rate = 90 liters / min, extrusion rate = 9g
/ Min, blow ratio = 1.8, take-up speed = 2.4 m / min,
A film having a thickness of 30 μm was inflation-molded under the processing temperature = 200 ° C.

Table 2 shows the melt properties and film properties of the ethylene copolymer composition.

[0126]

Reference Example 1 [Production of ethylene / α-olefin copolymer (C-1)] An ethylene / α-olefin copolymer was produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1. (C-1) was produced.

The ethylene / α-olefin copolymer composition (C-1) thus obtained had a density of 0.922 g / cm ³ and an MFR of 2.0 g / 10 minutes, and was produced in Example 1. It was similar to the ethylene-based copolymer composition.

[Film Processing] Using this ethylene / α-olefin copolymer (C-1), a film having a thickness of 30 μm was formed in the same manner as in Example 1. Ethylene / α
Table 2 shows the melt physical properties and film physical properties of the -olefin copolymer (C-1).

From Example 1 and Reference Example 1, the ethylene-based copolymer composition produced in Example 1 had the same density and MT.
And ethylene-α-olefin copolymer (C-1)
It can be seen that the obtained film is excellent in film impact, fluidity (FI) in a high shear region and blocking resistance as compared with.

[0130]

Comparative Example 1 [Preparation of Composition] In Production Example 1, bis (1-methyl-3)
-n-Butylcyclopentadienyl) zirconium dichloride
In place of the lid, the chi, described in Japanese Patent Publication No. 63-54289
Uses a tan-based catalyst component and replaces methylaluminoxane
The amount of comonomer is displayed using triethylaluminum.
Produced in the same manner as in Production Example 1 except that adjustments were made as shown in 1.
Ethylene / α-olefin copolymer produced (A-2)
(Density: 0.915g / cm³) And ethylene / α-ole
Fin copolymer (B-2) (density: 0.933 g / c
m ³) Is melt-kneaded at a weight ratio (A-2 / B-2) of 60/40.
To obtain an ethylene-based copolymer composition.

The density of the obtained ethylene copolymer composition was 0.922 g / cm ³ , and the MFR was 2.0 g / 10.
It was a minute. [Film Processing] Using this ethylene copolymer composition, a film having a thickness of 30 μm was formed in the same manner as in Example 1. Table 2 shows melt properties and film properties of the ethylene copolymer composition.

[0132]

[Comparative Example 2] [Production of ethylene / α-olefin copolymer (C-2)] An ethylene / α-olefin copolymer was prepared in the same manner as in Comparative Example 1 except that the comonomer content was adjusted as shown in Table 1. (C-2) was produced.

The ethylene / α-olefin copolymer obtained had a density of 0.922 g / cm ³ and an MFR of 1.9.
It was g / 10 minutes and was the same as the ethylene-based copolymer composition produced in Comparative Example 1.

[Film Processing] Using this ethylene / α-olefin copolymer (C-2), a film having a thickness of 30 μm was formed in the same manner as in Example 1. Ethylene / α
Table 2 shows the melt properties and film properties of the olefin copolymer (C-2).

From Comparative Example 1 and Comparative Example 2, it can be seen that the ethylene copolymer composition obtained in Comparative Example 1 is less improved in film impact and blocking resistance as compared with Example 1.

[0136]

[Table 1]

[0137]

[Table 2]

 ─────────────────────────────────────────────────── ─── 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-i) ethylene and α having 3 to 20 carbon atoms
-Copolymer with olefin, wherein (A-ii) density (d) is 0.880 to 0.940 g / cm ³
(A-iii) the intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is in the range of 1.0 to 10 dl / g, (A-iv) differential scanning calorimeter (DSC) The temperature (Tm (° C.)) at the maximum peak position and the density (d) in the endothermic curve measured by satisfying the relationship represented by Tm <400 × d-250, (A-v) the 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) decane-soluble part (W (wt%)) at room temperature The density (d) is an ethylene / α-olefin copolymer [A] of 5 to 95% by weight, which satisfies the relationship represented by W <80 × exp (−100 (d−0.88)) + 0.1. (B-i) 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
And (B-iii) the intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is 0.5 to 2 dl / g, and (B-iv) the differential scanning calorimeter (DSC). The temperature (Tm (° C.)) at the maximum peak position and the density (d) in the endothermic curve measured by Satisfy the relationship represented by Tm <400 × d-250, and (B-v) decane-soluble part at room temperature When (W (wt%)) and 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, which is an ethylene-based copolymer composition consisting of an ethylene / α-olefin copolymer [B] of 5 to 95% by weight, wherein (i) the above ethylene. Density of α-olefin copolymer [A] and the above ethylene / α-olefin copolymer [B]
The ratio ([A] / [B]) of the ethylene / α-olefin copolymer [B] is less than 1, and (ii) the intrinsic viscosity of the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B]. ] To the intrinsic viscosity ([η _A ] / [η _B ]) is 1 or more, and (iii) the density of the composition is 0.890 to 0.955 g / c.
in the range of ^{m 3, (iv) 190 ℃} , melt flow rate of the composition in 2.16kg load (MFR) is 0.1 to 100 g / 1
An ethylene-based copolymer composition characterized by being in the range of 0 minutes.