JPH07309909A - Ethylene copolymer composition - Google Patents

Abstract

PURPOSE:To obtain an ethylene copolymer composition which is excellent in moldability and gives a film excellent in transparency and mechanical strength, by mixing an ethylene/alpha-olefin copolymer produced by using a specified polymerization catalyst with crystalline polyolefins. CONSTITUTION:This composition consists of 60-99wt.% ethylene/a-olefin copolymer (A) and 1-40wt.% crystalline polyolefins (B). The component A is obtained by copolymerizing ethylene and a 3-20C alpha-olefin in the presence of an olefin polymerization catalyst containing an organoaluminumoxy compound, a transition metal compound represented by the formula ML<1>x (where M is a group IV transition metal atom; L<1> is a ligand coordinating to M; and x is the valence of M) and a transition metal compound represented by the formula ML<2>x (wherein M and x are as defined above; and L<2> is a ligand coordinating to M). The component B comprises (three specified) crystalline polyolefins, e.g. ethylene homopolymers having an MHR of 0.01-100g/10min at 190 deg.C under a load of 2.16kg and a density of above 0.900g/cm<3>.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an ethylene-based copolymer composition, and more particularly to an ethylene-based copolymer composition used as a material for films and the like.

[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 trying to mold blown film at high speed, the fluctuation of bubbles,
Alternatively, in order to stably perform high-speed molding without breaking, it is necessary to select an ethylene copolymer having a large melt tension (melt tension) for its molecular weight. 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 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 article such as a film is less sticky. However, since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Therefore, if an ethylene polymer having a high melt tension and excellent mechanical strength appears, its industrial value is extremely great.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is an ethylene copolymer composition capable of producing a film having excellent moldability, transparency and mechanical strength. The purpose is to provide things.

[0007]

SUMMARY OF THE INVENTION The ethylene copolymer composition according to the present invention comprises (A) (a) an organoaluminum oxy compound and (b-I) a transition metal compound represented by the following general formula [b-I]. At least one compound selected from the following: ML ¹ _X ... [b-I] (wherein M represents a transition metal atom selected from Group IVB of the periodic table, and L ¹ is coordinated with the transition metal atom M). At least two of these ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
It is an ethylcyclopentadienyl group or a substituted cyclopentadienyl group having at least one group selected from a hydrocarbon group having 3 to 10 carbon atoms, other than a (substituted) cyclopentadienyl group. The ligand L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X represents the valence of the transition metal atom M).
(B-II) containing at least one compound selected from the transition metal compounds represented by the following general formula [b-II], ML ² _X ... [b-II] (wherein M is a periodic table) A transition metal atom selected from Group IVB is shown, L ² is a ligand which coordinates to the transition metal atom, and at least two of the ligands L ² have a substituent. It is a ligand having a good cyclopentadienyl skeleton, and these groups are bound via a hydrocarbon group, a silylene group or a substituted silylene group, and have a ligand other than a ligand having a cyclopentadienyl skeleton. Order L ²
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X represents the valence of the transition metal atom M.) A mole of the transition metal compound (b-I) and the transition metal compound (b-II). Ratio [(b-I) / (b-II)] is 99
It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst in the range of / 1 to 80/20, and (i) has a density of 0.850 to 0. In the range of 980 g / cm ³ , (i
i) The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes, and (iii) the melt tension [MFR at 190 ° C.
T (g)] and melt flow rate [MFR (g / 10
Min)] is ⁶⁰ to 99% by weight of an ethylene / α-olefin copolymer satisfying the relationship of MT> 2.2 × MFR ^-0.84 , and (B) the following groups (B-I) to (B-III). 1 to 40% by weight of at least one crystalline polyolefin selected from the following: (B-I) a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg of 0.01 to 100 g / An ethylene homopolymer having a density of more than 0.900 g / cm ³ in the range of 10 minutes, or ethylene and 3 to 20 carbon atoms
Copolymer with α-olefin (excluding the ethylene / α-olefin copolymer (A)) (B-II) having a melt flow rate (MFR) of 0.1 at 230 ° C. and 2.16 kg load. To 100 g / 10 min and a density of more than 0.900 g / cm ³ , a propylene homopolymer or at least one olefin selected from propylene and ethylene and an α-olefin having 4 to 20 carbon atoms. Copolymer (B-III) having a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 100 g / 10 minutes and a density of more than 0.900 g / cm ³ and carbon. A homopolymer of α-olefin having 4 to 20 atoms, or a copolymer of α-olefin having 4 to 20 carbon atoms.

Such an ethylene copolymer composition is
Excellent moldability. A film excellent in transparency and mechanical strength can be produced from the ethylene-based copolymer composition of the present invention.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The ethylene copolymer composition according to the present invention will be described in detail below. The ethylene-based copolymer composition according to the present invention is formed from an ethylene / α-olefin copolymer (A) and a crystalline polyolefin (B).

Each component forming the ethylene copolymer composition according to the present invention will be described in detail. [Ethylene / α-olefin copolymer (A)] Ethylene / α forming the ethylene copolymer composition according to the present invention
-The olefin copolymer (A) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. 3 to 2 carbon atoms used for copolymerization with ethylene
As α-olefin of 0, 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. Of these, α-olefins having 3 to 10 carbon atoms are preferable, and α-olefins having 3 to 6 carbon atoms are more preferable.

Ethylene / α-olefin copolymer (A)
Then, the structural unit derived from ethylene is 50 to 100.
%, Preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight, and the structural unit derived from the α-olefin having 3 to 20 carbon atoms is 0 to 50% by weight, preferably 1 to
It is desirable to be present in a proportion of 45% by weight, more preferably 2-35% by weight, most preferably 4-30% by weight.

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

Such an ethylene / α-olefin copolymer (A) preferably has the following characteristics (i) to (iii), and the following (i) to (vii) It is more preferable to have the characteristics as shown.

(I) Density (d) is 0.850 to 0.9
80 g / cm ³ , preferably 0.880 to 0.940 g
/ Cm ³ , more preferably 0.890 to 0.935 g /
cm ³ , most preferably 0.900 to 0.930 g / c
It is desirable to be in the range of m 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 time, measurement is performed with a density gradient tube.

(Ii) The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is 0.01 to 200 g.
/ 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

Melt flow rate (MFR) is AST
It is measured under the conditions of 190 ° C. and 2.16 kg load according to M D1238-65T. (Iii) Melt tension at 190 ° C. [MT
(G)] and melt flow rate [MFR (g / 10 min)]
And MT> 2.2 × MFR ^−0.84, preferably 8.0 × MFR ^−0.84 >MT> 2.3 × MFR ^−0.84, more preferably 7.5 × MFR ^−0.84 >MT> 2.5 × MFR ^−0.84 It is desirable to satisfy the relationship shown in.

The ethylene / α-olefin copolymer having such characteristics has a large melt tension (MT) and good moldability. The melt tension (MT) is determined by measuring the stress when the melted 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, and the resin temperature is set to 190 by using an MT measuring machine manufactured by Toyo Seiki Seisakusho.
C, extrusion speed 15 mm / min, winding speed 10-20
m / min, nozzle diameter 2.09 mmφ, nozzle length 8 mm. At the time of pelletization, tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was previously added to the ethylene / α-olefin copolymer in an amount of 0.
05 wt%, n-octadecyl-3- (4 'as a heat stabilizer
0.1% by weight of -hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added.

(Iv) The stress at 190 ° C. is 2.4 × 1
The flow index [FI (1 / sec)] and the melt flow rate [MFR (g / 10 min)] defined by the shear rate when reaching 0 ⁶ dyne / cm ² are FI <150 × MFR, preferably FI. <140 × MFR More preferably, the relationship represented by FI <130 × MFR is preferably satisfied.

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 melt tension measurement, using a capillary flow characteristic tester manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C.,
The shear stress is measured in the range of 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

The diameter of the nozzle is changed as follows according to the MFR (g / 10 minutes) of the resin to be measured. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR (v) Molecular weight distribution measured by GPC ( _Mw / _Mn , where _Mw : weight average molecular weight, _Mn : number average molecular weight) is 1.
It is preferably in the range of 5 to 4.

The molecular weight distribution (M _w / M _n ) was measured as follows using GPC-150C manufactured by Millipore. The separation column is TSK GNH HT,
The column size is 72 mm in diameter and 600 mm in length,
The column temperature was 140 ° C, o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase, and BHT was used as the antioxidant.
(Takeda Pharmaceutical Co., Ltd.) 0.025% by weight was used, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of M _w <10.
00 and M _w > 4 × 10 ⁶ manufactured by Tosoh Corporation, and 1000 <M _w <4 × 10 ⁶ manufactured by Pressure Chemical Company.

(Vi) The temperature [Tm at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)]
(° C.)] and density [d (g / cm ³ )] are Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550 ×. It is desirable that the relationship represented by d-391 be satisfied.

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) was such that about 5 mg of a sample was packed in an aluminum pan and heated to 200 ° C. at 10 ° C./min. It is obtained from the endothermic curve when the temperature is lowered to room temperature at 20 ° C./min and then the temperature is raised at 10 ° C./min. Measured by Perkin Elmer DS
A C-7 type device was used.

(Vii) When the n-decane-soluble component amount fraction [W (wt%)] and density [d (g / cm ³ )] at room temperature are MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 W <60 × exp (−100 (d−0.88)) + 0.1 More preferably W <40 × exp (−100 (d− 0.88)) + 0.1 When MFR> 10 g / 10 minutes W <80 × (MFR-9) ^0.26 × exp (−100 (d−0.88)) + 0.1 The relationship is satisfied. .

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

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

Ethylene / α-having the above characteristics
The olefin copolymer (A) includes an organoaluminum oxy compound (a), a transition metal compound (b-I), a transition metal compound (b-II), a carrier, and, if necessary, an organoaluminum compound (c) described later. In the presence of an olefin polymerization catalyst formed from ethylene and an α-olefin having 3 to 20 carbon atoms, the resulting copolymer has a density of 0.8.
It can be produced by copolymerizing so as to have a concentration of 50 to 0.980 g / cm ³ .

Next, the organoaluminum oxy compound (a), which is a catalyst component used in the copolymerization of the ethylene / α-olefin copolymer (A) to form the ethylene-based copolymer composition of the present invention, the transition The metal compound (b-I), transition metal compound (b-II), carrier and organoaluminum compound (c) will be specifically described.

The organoaluminum oxy compound (a) (hereinafter sometimes referred to as “component (a)”) used in the copolymerization of the ethylene / α-olefin copolymer (A) in the present invention is It may be a conventionally known benzene-soluble aluminoxane, and JP-A-2-27680.
It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent Laid-Open No.

The conventionally known aluminoxane 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 adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the organoaluminum compound with adsorption water or crystallization water.

(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.

(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. Further, the solvent or the 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 when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. 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 ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

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

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

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

The solubility of such an organoaluminum oxy compound in benzene is 10 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 transition metal compound (b-I) used in the copolymerization of the ethylene / α-olefin copolymer (A) in the present invention is specifically a transition metal compound represented by the following formula [b-I]. Metal compound and transition metal compound (b-II)
Is a transition metal compound represented by the following formula [b-II].

ML ¹ _X (b-I) (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand coordinated to the transition metal atom M, At least two of these ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
It is an ethylcyclopentadienyl group or a substituted cyclopentadienyl group having at least one group selected from a hydrocarbon group having 3 to 10 carbon atoms, other than a (substituted) cyclopentadienyl group. The ligand L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is a valence of the transition metal atom M. ML ² _X ... [b-II] (wherein M represents a transition metal atom selected from Group IVB of the periodic table, L ² is a ligand coordinated to the transition metal atom, and among these, The at least two ligands L ² are ligands having a cyclopentadienyl skeleton which may have a substituent, and these groups are bonded via a hydrocarbon group, a silylene group or a substituted silylene group. are coupled Te, ligand L ² other than the ligand having a cyclopentadienyl skeleton
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
It is an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X represents the valence of the transition metal atom M).

The transition metal compound (b-I) represented by the general formula [b-I] and the transition metal compound (b-II) represented by the general formula [b-II] will be described more specifically below. explain.

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

L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are
Substituted cyclopentadienyl which is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or which has at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms. It is a base. These ligands may be the same or different. The ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and other substituents include a methyl group and an ethyl group. A group or a hydrocarbon group having 3 to 10 carbon atoms.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples thereof include alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll 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 atom is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms. A disubstituted cyclopentadienyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.

In the compound represented by the general formula [b-I], two (substituted) cyclopentadienyls coordinated to the transition metal atom M like the compound represented by the general formula [b-II] are used. The groups are not bound, such as via a hydrocarbon group.

In the above general formula [b-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,
It is an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

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

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

Examples of the aryloxy group include a phenoxy group and the like. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Halogen atoms are fluorine, chlorine, bromine and iodine. Examples of the transition metal compound represented by the general formula [b-I] 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-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylsik) Pentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium diethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (N-Butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) Examples thereof include zirconium phenyl chloride and bis (n-butylcyclopentadienyl) zirconium hydride chloride. 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. Further, 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 [b-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 above general formula [b-II], M is a transition metal atom selected from Group IVB of the periodic table, 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.

Of these ligands having a cyclopentadienyl skeleton, two ligands are bonded via a hydrocarbon group, a silylene group or a substituted silylene group. Examples of the hydrocarbon group include alkylene groups such as ethylene and propylene, and substituted alkylene groups such as isopropylidene and diphenylmethylene, and examples of the substituted silylene groups include dimethylsilylene group, diphenylsilylene group, and methylphenylsilylene group. .

In the above formula [b-II], the ligand L ² other than the ligand having the cyclopentadienyl skeleton coordinated to the transition metal atom M is the same as in the above formula [b-I]. It is a hydrocarbon group having 1 to 12 carbon atoms similar to L ¹ , an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

The transition metal compound represented by the general formula [b-II] is ethylene bis (indenyl).
Dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl zirconium monochloride, ethylene bis (indenyl) methyl zirconium monobromide, ethylene Bis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis {1- (4,5,6,7-tetrahydroindenyl)} dimethylzirconium, ethylenebis {1- (4,5,6, 7-Tetrahydroindenyl)} methyl zirconium monochloride, ethylenebis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dichloride, ethylenebis {1- (4,
5,6,7-Tetrahydroindenyl)} zirconium dibromide, ethylenebis {1- (4-methylindenyl)} zirconium dichloride, ethylenebis {1- (5-methylindenyl)} zirconium dichloride, ethylenebis { 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-dimethoxyindenyl)} zirconium dichloride, isopropylidene (cyclo Pentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl Renbisu (trimethyl cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium dichloride, and diphenyl (indenyl) zirconium dichloride. In the above example, the disubstituted cyclopentadienyl ring is 1,2- and 1,
3-substitutes are included, and tri-substitutes include 1,2,3- and 1,2,4-substitutes. 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 [b-II], ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, and diphenylsilylenebis (indenyl) zirconium dichloride are particularly preferable. preferable.

In the present invention, in producing the ethylene / α-olefin copolymer (A), at least one selected from the transition metal compounds represented by the above general formula [b-I] and the above general formula [b -II] in combination with at least one selected from transition metal compounds.

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.

At least one transition metal compound selected from the transition metal compounds (bI) represented by the above general formula [b-I] and the transition metal compound (b represented by the above general formula [b-II] -II) is at least one transition metal compound, and the molar ratio (bI / b-II) is 99/1 to 80/2.
It is desirable to use it in an amount of 0, preferably 97/3 to 82/18, and more preferably 95/5 to 85/15. With such a ratio, the above general formula [b-
I], at least one transition metal compound selected from the transition metal compounds (bI), and the above general formula [b-II]
By using at least one transition metal compound selected from the transition metal compounds (b-II) represented by the formula (3), an ethylene-based copolymer composition having excellent moldability, transparency and mechanical strength is obtained. It is possible to produce an ethylene / α-olefin copolymer (A) capable of forming When used in an amount such that the molar ratio (bI / b-II) is in the range of 95/5 to 85/15, ethylene / α- which can form an ethylene-based copolymer composition having particularly excellent transparency and mechanical strength. The olefin copolymer (A) can be produced.

Hereinafter, the term "component (b)" refers to at least one selected from the transition metal compounds (bI) represented by the above general formula [b-I] and the above general formula [b-II]. In some cases, it means a transition metal compound catalyst component containing at least one selected from the transition metal compounds (b-II).

The carrier used in the copolymerization of the ethylene / α-olefin copolymer (A) in the present invention is an inorganic or organic compound having a particle size of 10 to 300 μm.
m, preferably 20 to 200 μm, in the form of granules or fine particles are used. Among these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, Z
nO, BaO, ThO _2, etc. or a mixture thereof such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —Ti
O ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -T
For example, iO ₂ -MgO can be used. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter if it contains a carbonate, a sulfate, a nitrate, or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a carrier vary depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 1
0 to 700 m ² / g and a pore volume of 0.3 to 2.
It is preferably 5 cm ³ / g. The carrier is, if necessary, 100 to 1000 ° C., preferably 150 to 700.
It is used after firing at ℃.

In such a carrier, it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.5 to 4%. 0.0% by weight, particularly preferably 2.0 to 3.5
It is desirable that the content is wt%.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the carrier are determined as follows. [Amount of adsorbed water] The amount of weight loss when dried for 4 hours under normal pressure and nitrogen flow at a temperature of 200 ° C is determined, and the percentage of the weight before drying is taken as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at 200 ° C. under normal pressure and nitrogen flow for 4 hours, and the carrier is further baked at 1000 ° C. for 20 hours. The weight is calculated by the following formula, where Y (g) is the weight of the baked product from which the surface hydroxyl groups disappear.

Surface hydroxyl group amount (% by weight) = {(X−Y) / X} × 100 Further, as a carrier that can be used in the present invention, a granular or fine particle of an organic compound having a particle size of 10 to 300 μm is used. The solid form may be mentioned. Examples of these organic compounds include (co) polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or vinylcyclohexane, styrene. The polymer or copolymer produced by using as a main component can be exemplified.

The catalyst used in the copolymerization of the copolymer (A) in the present invention is the organoaluminum oxy compound (a), the transition metal compound (b-I) or the transition metal compound (b).
-II), and a carrier, but may optionally include (c) an organoaluminum compound.

Examples of the (c) organoaluminum compound (hereinafter sometimes referred to as “component (c)”) which is optionally used include organoaluminum compounds represented by the following general formula [IV]. can do.

R ¹ _n AlX _3-n ... [IV] (In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n represents 1 to 1).
It is 3. In the above general formula [IV], 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 -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Such an organoaluminum compound (c)
Specifically, the following compounds may be mentioned. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum 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 the organoaluminum compound (c), a compound represented by the following general formula [V] can be used. R ¹ _n AlY _3-n ... [V] (In the formula, R ¹ is the same as above, Y is a —OR ² group,
OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -SiR
⁶ ₃ groups or —N (R ⁷ ) AlR ⁸ ₂ groups, and n is 1 to 2
And 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, an isopropyl group. , Phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) Specific examples of such an organoaluminum compound include the following compounds. (1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ A
l (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiE
t _{3), ^{etc.; (3) R 1 n Al}} (OAlR 4 2) a compound represented by _3-n,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlO
Al (iso-Bu) _{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 Al
NHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂
AlN (SiMe ₃ ) _{2 and the} like; (5) Compounds represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) R ¹ _n Al (N ( R ⁷ ) AlR ⁸ ₂ ) _3-n represented by a compound such as Et ₂ AlN (Me) AlEt ₂ , (i
so-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

[0077] Among the above general formula [IV] and an organoaluminum compound represented by [V], the general formula R ¹ ₃ Al, R
^The compounds represented by ¹ _n Al (OR ² ) _3-n and R ¹ _n Al (OAlR 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 copolymer (A) is produced, the above-mentioned component (a), component (b) and carrier and, if necessary, component (c) are brought into contact with each other. The catalyst thus prepared is preferably used. At this time, the order of contacting the components (a) to (c) and the carrier is arbitrarily selected, but preferably the carrier and the component (a) are mixed and contacted, and then the component (b) is mixed and contacted. If necessary, the component (c) is mixed and brought into contact. In addition, the component (b) forms the component (b) 2
It is preferred that one or more kinds of transition metal compounds are premixed and then mixed and contacted with other components.

The contact between the above-mentioned components (a) to (c) and the carrier can be carried out in an inert hydrocarbon medium. Specifically, as the inert hydrocarbon medium used for preparing the catalyst, propane, Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene; Examples thereof include halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof.

When the component (a), the component (b), the carrier and, if necessary, the component (c) are mixed and contacted, the component (b) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ per 1 g of the carrier. The amount of the component (b) used is about 10 ^-4 to 2 × 10 ^-2 mol / mol, preferably 10 ^{-5 to} 2 × 10 ^-4 mol.
It is in the range of liter (medium), preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / liter (medium). The atomic ratio (Al / transition metal) of aluminum of the component (a) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 20.
It is 0. The atomic ratio (Al-c / Al-a) of the aluminum atom (Al-c) of the component (c) and the aluminum atom (Al-a) of the component (a) which are used as necessary is usually 0.02.
-3, preferably 0.05-1.5. The mixing temperature for mixing and contacting the component (a), the component (b) and the carrier, and optionally the component (c) is usually -50 to 1.
The temperature is 50 ° C., preferably −20 to 120 ° C., and the contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

The olefin polymerization catalyst (solid catalyst component) thus obtained has 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom of transition metal atom derived from the component (b) per 1 g of the carrier. It is preferably supported in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ gram atom, and 10 ^{−3 to} 5 × 10 10 aluminum atoms derived from the component (a) and the component (c) per 1 g of the carrier.
It is desirable to support in an amount of ^-2 gram atom, preferably 2 x 10 ^-3 to 2 x 10 ^-2 gram atom.

Ethylene / α-olefin copolymer (A)
The olefin polymerization catalyst used for the production of the above is a prepolymerized catalyst obtained by prepolymerizing olefin in the presence of the above-mentioned component (a), component (b), carrier and, if necessary, component (c). May be The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon medium in the presence of the component (a), the component (b) and the carrier as described above, and optionally in the coexistence of the component (c). You can

The solid catalyst component is preferably formed from the components (a) and (b) and the carrier.
In this case, in addition to the solid catalyst component, the component (a) and / or the component (c) not supported on the carrier may be added.

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-dodecene, 1-tetradecene and the like can be exemplified. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

In the prepolymerization, the above component (b) is
It is usually 1 in terms of the transition metal atom derived from the component (b).
It is used in an amount of 0 ^{−6 to} 2 × 10 ⁻² mol / liter (medium), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (medium), and the component (b) is usually 5 per 1 g of the carrier. × 10 ^{-6 to} 5
It is used in an amount of × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. The atomic ratio (Al / transition metal) between the component (a) aluminum and the component (b) transition metal is usually 10
~ 500, preferably 20-200. Aluminum atom (Al-c) of component (c) that is used as necessary
The atomic ratio (Al-c / Al-a) of the aluminum atom (Al-a) of the component (a) is usually 0.02 to 3, preferably 0.05 to 1.5. Prepolymerization temperature is -20
To 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The prepolymerization catalyst is prepared, for example, as follows. That is, the carrier is suspended in an inert hydrocarbon. Next, an organoaluminum oxy compound [component (a)] 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 (b)] is added to the system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound [component (c)], and an olefin is introduced therein to produce a preliminary polymerization catalyst by preliminary polymerization. The olefin polymer is 0.1 to 50 per 1 g of the carrier.
It is desirable that the amount is 0 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g. In the prepolymerization catalyst, the amount of the component (b) as a transition metal atom is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atom per 1 g of the carrier. The aluminum atom (Al) derived from the component (a) and the component (c) is a transition metal atom (M) derived from the component (b).
It is desirable that the carrier is supported in an amount in the range of 5 to 200, preferably 10 to 150 in terms of molar ratio (Al / M).

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,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

The ethylene / α-olefin copolymer (A) forming the ethylene-based copolymer composition of the present invention contains ethylene and 3 carbon atoms in the presence of the above catalyst.
To 20 α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-It is obtained by copolymerizing with 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 medium, or the olefin itself may be used as the medium.

Specific examples of the inert hydrocarbon medium used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples include petroleum fractions such as gasoline, kerosene, and light oil. 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 polymerization, in addition to the organoaluminum oxy compound [component (a)] and the organoaluminum compound [component (c)] supported on the carrier, the organoaluminum oxy compound and / or the organic aluminum oxy compound and / or the organic aluminum oxy compound not supported on the carrier are further added. An aluminum compound may be used. In this case, the atomic ratio of the aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and / or the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound [component (b)] ( A
1 / M) is in the range of 5-300, preferably 10-200, more preferably 15-150.

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. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

[Crystalline Polyolefin (B)] The crystalline polyolefin used in the present invention will be specifically described below. The crystalline polyolefin [B] forming the ethylene-based copolymer composition according to the present invention includes the following (B-I) to
It is at least one crystalline polyolefin selected from (B-III).

Crystalline Polyolefin (B-I) The crystalline polyolefin (B-I) is an ethylene homopolymer having a crystallinity of 65% or more measured by an X-ray diffraction method,
Or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, having a degree of crystallinity of 65% or more,
The melt flow rate (MFR) at 0 ° C. under a load of 2.16 kg is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, and the density is 0.90.
More than 0 g / cm ³ , preferably 0.930 to 0.97
It is preferably in the range of 0 g / cm ³ .

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-
Mention may be made of hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, it is particularly preferable to use an α-olefin having 3 to 10 carbon atoms. In such a copolymer, the molar ratio of ethylene and α-olefin (ethylene / α-olefin) is generally 100/0 to 99/1, preferably 100, though it varies depending on the type of α-olefin. / 0-9
It is 9.5 / 0.5.

The crystalline polyolefin (B-I) is
A component unit other than the α-olefin-derived component unit such as a diene compound-derived component unit may be contained within a range that does not impair the characteristics.

Examples of component units other than the component units derived from such α-olefins include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl- Chain non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5- Methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl
Cyclic non-conjugated dienes such as 2-norbornene; Diene compounds such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene The component units derived from can be mentioned.

The diene components can be used alone or in combination. The content of the diene component is
It is usually 0 to 1 mol%, preferably 0 to 0.5 mol%. Such crystalline polyolefin (B-I) can be produced by a conventionally known method.

As the crystalline polyolefin (B-I), crystalline polyolefin excluding the ethylene / α-olefin copolymer (A) is used. Crystalline Polyolefin (B-II) The crystalline polyolefin (B-II) is a propylene homopolymer having a crystallinity of 50% or more measured by X-ray diffractometry, or propylene, ethylene and 4 carbon atoms.
To a copolymer of at least one olefin selected from α-olefins having an crystallization degree of 30%.
The above-mentioned copolymer has a melt flow rate (MFR) of 0.1 to 100 at 230 ° C. and a load of 2.16 kg.
g / 10 min, preferably in the range of 0.5 to 50 g / 10 min, a density of greater than 0.900 g / cm ^3, it is desirable that preferably in the range of 0.900~0.920g / cm ³ .

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-
Mention may be made of methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, it is particularly preferable to use an α-olefin having 4 to 10 carbon atoms.

In the copolymer of propylene and at least one selected from ethylene and α-olefins having 4 to 20 carbon atoms, the molar ratio of propylene to ethylene and α-olefins having 4 to 20 carbon atoms is set. [Propylene / α-olefin (excluding propylene)] is generally 100/0, although it varies depending on the type of α-olefin.
90/10, preferably 100/0 to 95/5.

The crystalline polyolefin (B-II) is
A component unit derived from the diene compound used for the crystalline polyolefin (B-I) as described above may be contained within a range that does not impair the characteristics. The content of the diene component is usually 0 to 1 mol%, preferably 0 to 0.5.
Mol%.

Such crystalline polyolefin (B-II)
Can be produced by a conventionally known method. Crystalline Polyolefin (B-III) The crystalline polyolefin (B-III) has 4 to 20 carbon atoms and has a crystallinity of 30% or more measured by an X-ray diffraction method.
A homopolymer of 20 α-olefins or a copolymer of α-olefins having 4 to 20 carbon atoms and having the same degree of crystallinity of 30% or more, and a melt flow rate at 230 ° C. under a load of 2.16 kg ( MFR) is 0.1-100g
/ 10 min, preferably in the range of 0.5 to 50 g / 10 min, a density of greater than 0.900 g / cm ^3, it is desirable that preferably in the range of 0.900~0.920g / cm ^3.

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-
Mention may be made of methyl-1-pentene, 1-octene, 1-decene. Of these, it is particularly preferable to use an α-olefin having 4 to 10 carbon atoms.

At least two or more carbon atoms having 4 to 20 carbon atoms
The α-olefin copolymer of
Molar ratio [(a) of one α-olefin (a) selected from α-olefins having 20 to 20 carbon atoms and another α-olefin (b) selected from α-olefins having 4 to 20 carbon atoms]
/ (B)] varies depending on the type of α-olefin, but is generally 100/0 to 90/10, preferably 100
/ 0 to 95/5.

Crystalline polyolefin (B-III)
May contain a component unit or the like derived from the diene compound used in the crystalline polyolefin (B-I) as described above, as long as the characteristics thereof are not impaired. The content of the diene component is usually 0 to 1 mol%, preferably 0 to
It is 0.5 mol%.

Such crystalline polyolefin (B-II
I) can be produced by a conventionally known method. [Ethylene Copolymer Composition] The ethylene copolymer composition according to the present invention comprises the ethylene / α-olefin copolymer (A) and the crystalline polyolefin (B), and ethylene / α- Weight ratio of olefin copolymer (A) and crystalline polyolefin (B) [(A) :( B)]
Is preferably in the range of 99: 1 to 60:40,
More preferably, it is in the range of 95: 5 to 70:30,
Particularly preferably, it is desirable to be in the range of 95: 5 to 80:20. Further, the ethylene / α-olefin copolymer (A) and the crystalline polyolefin (B) have a ratio of the density of the crystalline polyolefin (B) to the density of the ethylene / α-olefin copolymer (A) [ (B) / (A)] is 1
Less than, preferably 0.905 to 0.980.

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) A method of mechanically blending the ethylene / α-olefin copolymer (A), the crystalline polyolefin (B), and optionally other components with an extruder or a kneader.

(2) The ethylene / α-olefin copolymer (A), the crystalline polyolefin (B), and optionally other components are combined with a suitable good solvent (eg, hexane, heptane, decane, cyclohexane, benzene,
Dissolved in a hydrocarbon solvent such as toluene and xylene),
Then a method of removing the solvent.

(3) After preparing a solution in which the ethylene / α-olefin copolymer (A), the crystalline polyolefin (B), and optionally other components added are separately dissolved in a suitable good solvent, A method of mixing 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 can be used for ordinary air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, T-
A film can be obtained by processing by die film molding, water-cooled inflation molding or the like. The film thus formed has an excellent balance of transparency and rigidity, and has the heat sealability, hot tack property, heat resistance and the like which are the features of ordinary LLDPE. Further, since the composition distribution of the ethylene / α-olefin copolymer is extremely narrow, the film surface is not sticky. Furthermore, since the melt tension is high, the bubble stability during inflation molding is excellent.

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. Further, it can be used for blow infusion bags, blow bottles, tubes formed by extrusion, pipes, tear-off caps, injection molded products such as daily sundries, fibers, and large molded products formed by rotational molding.

[0116]

The ethylene-based copolymer composition of the present invention is
It is obtained by copolymerizing ethylene and an olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound and at least two specific transition metal compounds, and has specific physical properties. Since it is formed from ethylene / α-olefin copolymer and crystalline polyolefin, it has excellent moldability. A film having excellent mechanical strength such as transparency and tensile strength can be produced from such an ethylene-based copolymer composition.

[0117]

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

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

[Tensile Test] A dumbbell (JIS No. 1) was used to punch a test piece in the machine direction (MD) and the transverse direction (TD) with respect to the film forming direction, and the chuck distance was 86 m.
m, crosshead speed 200 mm / min. The tensile modulus (YM) and the elongation at break (EL) were measured by.

[0120]

[Production Example 1] Polymerization of ethylene / 1-butene copolymer (A-1) [Preparation of catalyst component] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 liters of toluene, Cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) 2
8.7 liters were added dropwise in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Then, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and at that temperature, 4
Reacted for 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 80 liters of toluene. Into this system, a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and a toluene solution of ethylenebis (indenyl) zirconium dichloride ( Zr; 1.92 mmol / liter) (14.6 liters) was added dropwise at 80 ° C over 30 minutes, and the mixture was further reacted at 80 ° C for 2 hours. Then, the supernatant was removed, and the solid was washed twice with hexane to obtain a solid catalyst (a) containing 3.4 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst] To 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst (a) obtained above and 76.5 g of 1-hexene were added, By carrying out a prepolymerization of ethylene at 35 ° C. for 2 hours, 3 g / g of the solid catalyst can be obtained.
Prepolymerization catalyst (b) in which g of polyethylene was prepolymerized
Got

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. The prepolymerized catalyst prepared above was converted into zirconium atoms at 0.17 mmol / h and triisobutylaluminum at 10 mmol / h.
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.028, hydrogen / ethylene = 5.2 × 10 ⁻⁴ , ethylene concentration = 25%).

The yield of the ethylene / 1-hexene copolymer (A-1) thus obtained was 6.1 kg / h, the MFR was 2.0 g / 10 min, and the density was 0.922.
g / cm ³ , the decane-soluble part at room temperature is 0.2
It was 3% by weight. Ethylene / 1-hexene copolymer (A
The physical properties of -1) are shown in Table 1.

[0125]

Reference Example 1 Using the ethylene / 1-butene copolymer (A-1) obtained in Production Example 1, 20 mmφ · L / D = 26
Single screw extruder, 25mmφ die, lip width 0.7m
m, using a single slit air ring, air flow rate = 90 liters / minute, extrusion rate = 9 g / minute, blow ratio = 1.8, take-up speed = 2.4 m / minute, processing temperature = 200 ° C, thickness A 30 μm film was inflation molded.

The melt properties and film properties of the copolymer are shown in Table 3.

[0127]

[Example 1] Ethylene 1- produced according to the above Production Example 1
Mixing ratio (A-1 / B-1) = hexene copolymer (A-1) and crystalline polyolefin (B-1) shown in Table 2
Dry blended at 90/10, and 0.05 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant, heat-resistant stabilizer to 100 parts by weight of resin part. N-octadecyl-3- (4'-hydroxy-3 ', as
0.1 parts by weight of 5'-di-t-butylphenyl) propionate and calcium stearate as a hydrochloric acid absorbent were added in an amount of 0.1 part by weight.
05 parts by weight were compounded. After that, a conical taper type twin-screw extruder manufactured by Haake Co. was used and kneaded at a set temperature of 180 ° C. to obtain an ethylene copolymer composition.

Using the ethylene-based copolymer composition obtained above, a film having a thickness of 30 μm was inflation-molded in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0129]

Example 2 The ethylene / 1-butene copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-2) shown in Table 2 were mixed in a mixing ratio (A-1 / B-2). = 90/10
Was dry-blended and melt-kneaded in the same manner as in Example 1 to obtain an ethylene-based copolymer composition.

Using this ethylene-based copolymer composition,
A film having a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0131]

Example 3 A mixing ratio (A-1 / B-3) of the ethylene / 1-butene copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-3) shown in Table 2 was used. = 90/10
Was dry-blended and melt-kneaded in the same manner as in Example 1 to obtain an ethylene-based copolymer composition.

Using this ethylene-based copolymer composition,
A film having a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0133]

Example 4 The ethylene / 1-butene copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-4) shown in Table 2 were mixed at a mixing ratio (A-1 / B-4). = 90/10
Was dry-blended and melt-kneaded in the same manner as in Example 1 to obtain an ethylene-based copolymer composition.

Using this ethylene-based copolymer composition,
A film having a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0135]

Example 5 The ethylene / 1-butene copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-5) shown in Table 2 were mixed in a mixing ratio (A-1 / B-5). = 90/10
Was dry-blended and melt-kneaded in the same manner as in Example 1 to obtain an ethylene-based copolymer composition.

Using this ethylene-based copolymer composition,
A film having a thickness of 30 μm was formed by inflation molding in the same manner as in Reference Example 1. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

The compositions obtained in Examples 1 to 5 were excellent in fluidity (FI) in the high shear region as compared with the ethylene / 1-hexene copolymer (A-1), and the obtained films were obtained. Shows that the film has excellent rigidity as compared with the film formed from the ethylene / 1-hexene copolymer (A-1).

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Todo 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

[Claims] ^1. ML ¹ _X , and (A) (a) an organoaluminum oxy compound, (b-I) at least one compound selected from transition metal compounds represented by the following general formula [b-I]: [B-I] (In the formula, M represents a transition metal atom selected from Group IVB of the periodic table, L ¹ represents a ligand coordinated to the transition metal atom M, and at least two of them are represented. The ligand L ^{1 of} is a cyclopentadienyl group, a methylcyclopentadienyl group,
It is an ethylcyclopentadienyl group or a substituted cyclopentadienyl group having at least one group selected from a hydrocarbon group having 3 to 10 carbon atoms, other than a (substituted) cyclopentadienyl group. The ligand L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X represents the valence of the transition metal atom M).
(B-II) containing at least one compound selected from the transition metal compounds represented by the following general formula [b-II], ML ² _X ... [b-II] (wherein M is a periodic table) A transition metal atom selected from Group IVB is shown, L ² is a ligand which coordinates to the transition metal atom, and at least two of the ligands L ² have a substituent. It is a ligand having a good cyclopentadienyl skeleton, and these groups are bound via a hydrocarbon group, a silylene group or a substituted silylene group, and have a ligand other than a ligand having a cyclopentadienyl skeleton. Order L ²
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X represents the valence of the transition metal atom M.) A mole of the transition metal compound (b-I) and the transition metal compound (b-II). Ratio [(b-I) / (b-II)] is 99
It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst in the range of / 1 to 80/20, and (i) has a density of 0.850 to 0. In the range of 980 g / cm ³ , (i
i) The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes, and (iii) the melt tension [MFR at 190 ° C.
T (g)] and melt flow rate [MFR (g / 10
Min)] is ⁶⁰ to 99% by weight of an ethylene / α-olefin copolymer satisfying the relationship of MT> 2.2 × MFR ^-0.84 , and (B) the following groups (B-I) to (B-III). 1 to 40% by weight of at least one crystalline polyolefin selected from the group (1) above;
(B-I) an ethylene homopolymer having a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg in the range of 0.01 to 100 g / 10 min and a density of more than 0.900 g / cm ³ , or Ethylene and 3 to 20 carbon atoms
Copolymer with α-olefin (excluding the ethylene / α-olefin copolymer (A)) (B-II) having a melt flow rate (MFR) of 0.1 at 230 ° C. and 2.16 kg load. To 100 g / 10 min and a density of more than 0.900 g / cm ³ , a propylene homopolymer or at least one olefin selected from propylene and ethylene and an α-olefin having 4 to 20 carbon atoms. Copolymer with (B-III) 230
Melt flow rate (M
FR) is in the range of 0.1 to 100 g / 10 minutes and the density is more than 0.900 g / cm ^3, and is a homopolymer of α-olefin having 4 to 20 carbon atoms, or 4 to 2 carbon atoms.
A copolymer of 0 α-olefins.