JP3365682B2 - Ethylene copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to an ethylene copolymer composition.
For things, more specifically, as a material such as a film
It relates to the ethylene copolymer composition used.
You. [0002] BACKGROUND OF THE INVENTION Ethylene-based copolymers
It is formed by a shaping method and is used for various purposes.
Ethylene copolymers are required depending on the molding method and application.
The characteristics to be obtained are different. For example, inflation
When trying to mold film at high speed,
Or for stable high-speed molding without tearing
Is a melt-based polymer for its molecular weight as an ethylene copolymer.
Must select a material with a large solution (melt tension).
No. Similar characteristics of sag or down in hollow molding
To prevent tearing or in T-die molding
It is necessary to minimize the width drop. In addition
Extrusion molding such as
The low stress of ethylene-based copolymers
It is necessary from the economical aspects such as quality improvement and reduction of power consumption during molding.
is there. [0003] Incidentally, Ziegler type catalysts, especially titanium
Tension and swelling of ethylene polymer obtained using
Ratio (die-well ratio) to improve moldability
The method is described in JP-A-56-90810 or JP-A-56-90810.
It is proposed in, for example, JP-A-60-106806. Only
And ethylene-based heavyweight generally obtained using a titanium-based catalyst.
In the coalesced, especially low-density ethylene copolymer, the composition distribution is
Widely, molded products such as films are sticky.
There was a title. Among the Ziegler type catalyst systems, metallocene catalysts
The composition distribution of the ethylene polymer obtained using
It is long and the molded body such as film is less sticky
It is known that there is a place. However, the molecular weight
Due to the small size of the cloth, poor fluidity during extrusion is a concern.
To be reminded. For this reason, if the melt tension is high,
The emergence of ethylene polymers with excellent mechanical strength
If so, its industrial value is extremely large. [0006] OBJECTS OF THE INVENTION The present invention has been developed in view of the above situation.
It has excellent moldability, and has excellent optical properties and / or
Or it is possible to produce a film with excellent mechanical strength
For the purpose of providing an ethylene copolymer composition
I have. [0007] SUMMARY OF THE INVENTION The ethylene copolymer composition according to the present invention
Is (I) (a) an organic aluminum oxy compound, and (b-
I) From a transition metal compound represented by the following general formula [b-I]
At least one compound selected from: ML¹ _X      … [B-I] (Where M is a transition metal source selected from Group IVB of the periodic table)
Indicates a child, L¹Represents a ligand coordinated to the transition metal atom M
And at least two of these ligands L¹Is a shik
Lopentadienyl group, methylcyclopentadienyl group,
An ethylcyclopentadienyl group or a carbon source
At least one selected from hydrocarbon groups having 3 to 10 carbon atoms
A substituted cyclopentadienyl group having the group
Exchange) ligand L other than cyclopentadienyl group¹Is carbon
C1-C12 hydrocarbon group, alkoxy group, arylo
Xy group, trialkylsilyl group, halogen atom or water
And X represents the valence of the transition metal atom M) (B-II) a transition metal compound represented by the following general formula [b-II]
At least one compound selected from the group consisting of ML^Two _X      … [B-II] (Where M is a transition metal source selected from Group IVB of the periodic table)
Indicates a child, L^TwoIs a ligand that coordinates to the transition metal atom.
And at least two of these ligands L^TwoReplace
Having a cyclopentadienyl skeleton which may have a group
These groups include hydrocarbon groups, silylene
Group or substituted silylene group,
Ligands other than ligands having a lopentadienyl skeleton L^Two
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
Aryloxy group, trialkylsilyl group, halogen atom
Or a hydrogen atom, and X represents the valence of the transition metal atom M.
Shown) The transition metal compound (b-I) and the transition metal compound
The molar ratio with the product (b-II) [(b-I) / (b-II)] is 99
/ 1 to 80/20 of the catalyst for olefin polymerization
In the presence of ethylene and α-olefin with 3 to 20 carbon atoms
Obtained by copolymerizing (I) Density is 0.850 to 0.980 g / cm^ThreeRange
In (Ii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.4 to 8 dl / g, (Iii) Melt tension at 190 ° C. [MT
(G)] and melt flow rate [MFR (g / 10 min)]
But MT> 2.2 × MFR^-0.84 Ethylene / α-olefin copolymer weight satisfying the relationship shown by
(A) 20 to 90% by weight of (A) organic aluminum
Muoxy compound and (b ') cyclopentadienyl skeleton
Group IV transition metal compounds containing ligands with
Ethylene and carbon in the presence of an olefin polymerization catalyst containing
Copolymerization with an α-olefin having 3 to 20 element atoms.
And obtained by (I) Density is 0.850 to 0.980 g / cm^ThreeRange
In (Ii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Ethylene-α-olef in the range of 0.4 to 8 dl / g
Of ethylene copolymer (B) in an amount of 10 to 80% by weight
Α-olefin copolymer composition (excluding ethylene
・ Α-olefin copolymer (A) and ethylene α-olefin
Is not the same as the copolymer (B)). (II) Melt flow at 190 ° C and 2.16 kg load
-Rate (MFR) in the range of 0.01 to 100 g / 10 minutes
From low-density polyethylene by high-pressure radical method in Japan
The above (I) ethylene / α-olefin copolymer group
Weight ratio of the product to the above (II) low density polyethylene
[(I) :( II)] is in the range of 99: 1 to 60:40.
It is characterized by that. [0008] Such an ethylene copolymer composition comprises:
Excellent moldability. Ethylene copolymer composition of the present invention
From the object, excellent in optical properties and / or mechanical strength
Films can be manufactured. [0009] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the ethylene-based copolymer of the present invention will be described.
The polymer composition will be specifically described. According to the present invention
The ethylene-based copolymer composition is ethylene-α-olefin
Copolymer (A) and ethylene / α-olefin copolymer
(B) an ethylene / α-olefin copolymer set
Product (I) and low density polyethylene by high pressure radical method
It is formed from ren (II). The ethylene copolymer composition according to the present invention is
Each component to be formed will be described in detail. [Ethylene / α-olefin copolymer (A)]
Ethylene-α forming such an ethylene-based copolymer composition
-Olefin copolymer (A) is composed of ethylene and carbon atoms
A random copolymer with 3 to 20 α-olefins
You. 3 to 2 carbon atoms used for copolymerization with ethylene
As the α-olefin of 0, propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-1-pentene, 1-octane
Ten, 1-decene, 1-dodecene, 1-tetradecene, 1-hex
Sadecene, 1-octadecene, 1-eicosene, etc.
It is. Among these, α-olefins having 3 to 10 carbon atoms
And α-olefins having 3 to 6 carbon atoms are preferred.
More preferred. [0011] Ethylene / α-olefin copolymer (A)
Then, the structural unit derived from ethylene is 50 to 100
% By weight, preferably 55-99% by weight, more preferably
65-98% by weight, most preferably 70-97% by weight
Α-olefin with 3-20 carbon atoms
The structural unit derived therefrom is 0 to 50% by weight, preferably 1 to 50% by weight.
45% by weight, more preferably 2-35% by weight, most preferably
Or 3 to 30% by weight.
No. Composition of ethylene / α-olefin copolymer
Is about 200 mg of copolymer in a 10 mmφ sample tube.
Dissolve the body uniformly in 1 ml of hexachlorobutadiene
Sample¹³The C-NMR spectrum was measured at a measurement temperature of 120.
° C, measurement frequency 25.05 MHz, spectrum width 150
0 Hz, pulse repetition time 4.2 sec., Pulse width 6 μse
It is determined by measuring under the measurement conditions of c. Such ethylene / α-olefin copolymers
The coalescing (A) has the following properties (i) to (iii)
And preferably has the following (i) to (vi)
It is more preferable to have such characteristics. (I) The density (d) is 0.850 to 0.9.
80g / cm^Three, Preferably 0.880 to 0.940 g
/ Cm^Three, More preferably 0.890 to 0.935 g /
cm^Three, Most preferably 0.900 to 0.930 g / c
m^ThreeIs desirably within the range. The density (d) is 2.
When measuring melt flow rate (MFR) with 16kg load
The strand obtained in (1) is heat-treated at
After slowly cooling to room temperature over time, measure with a density gradient tube.
You. (Ii) The pole measured at 135 ° C. in decalin
The limiting viscosity [η] is 0.4 to 8 dl / g, preferably 1.25
~ 8 dl / g, more preferably in the range of 1.27-6 dl / g
Is desirable. (Iii) Melt tension at 190 ° C.
[MT (g)] and melt flow rate [MFR (g /
10 minutes)] 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 by. Ethylene α-O having such properties
Refin copolymer has high melt tension (MT)
The properties are good. The melt tension (MT) is
Measuring the stress when stretching the stretched polymer at a constant speed.
Is determined by That is, the produced polymer powder passes
Melt and pelletize in the usual manner to obtain a measurement sample.
Using an MT measuring machine manufactured by YOSEIKI SEISAKUSHO, resin temperature 190
° C, extrusion speed 15mm / min, winding speed 10-20
m / min, nozzle diameter 2.09mmφ, nozzle length 8mm
Performed under conditions. When pelletizing, ethylene / α-ole
The fin copolymer is preliminarily used as a secondary antioxidant.
Poly (2,4-di-t-butylphenyl) phosphate is added to 0.
05% by weight, n-octadecyl-3- (4 ′
-Hydroxy-3 ', 5'-di-t-butylphenyl) propionate
0.1% by weight of stearic acid as a hydrochloric acid absorbent
0.05% by weight of lucium was added. The melt flow rate (MFR) is AST
According to MD1238-65T, the condition of 190 ℃, 2.16kg load
Measured below. (Iv) Stress at 190 ° C. is 2.4 × 10⁶dyne / c
m^TwoFlow index as defined by the shear rate at which
[FI (1 / second)] and melt flow rate [MFR
(G / 10 minutes)] FI <150 × MFR Preferably FI <140 × MFR More preferably, FI <130 × MFR It is desirable to satisfy the relationship shown by. The fluidity index (FI) is
While changing the speed, extrude the resin from the capillary and
Is determined by measuring the stress at the time. Sand
Using the same sample as for the melt tension measurement, Toyo Seiki Seisakusho
Using a capillary flow characteristics tester, resin temperature 190 ° C,
The range of shear stress is 5 × 10^Four~ 3 × 10⁶dyne / cm^TwoAbout
Measured in degrees. Note that the MFR (g / 10 minutes) of the resin to be measured is
Therefore, the measurement is performed by changing the diameter of the nozzle as follows. 0.5 mm when MFR> 20 1.0mm when 20 ≧ MFR> 3 2.0mm when 3 ≧ MFR> 0.8 3.0mm when 0.8 ≧ MFR (V) Endotherm measured by differential scanning calorimeter (DSC)
Temperature [Tm (° C.)] and density [d at the maximum peak position of the curve
(G / cm^Three)] Tm <400 × d-250 Preferably, Tm <450 × d-297 More preferably, Tm <500 × d-344. Particularly preferably, Tm <550 × d-391 It is desirable to satisfy the relationship shown by. The measurement was made by a differential scanning calorimeter (DSC).
The temperature (Tm) at the maximum peak position of the determined endothermic curve is
About 5 mg into an aluminum pan at 10 ° C / min to 200 ° C.
And then hold at 200 ° C for 5 minutes, then at 20 ° C / min.
Endotherm when cooling down to room temperature and then heating at 10 ° C / min
Obtained from the curve. The measurement was made by PerkinElmer DS
A C-7 type device was used. (Vi) n-decane soluble component at room temperature
Rate [W (% by weight)] and density [d (g / cm^Three)] When MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9)^0.26× exp (−100 (d−
0.88)) + 0.1 Satisfies the relationship indicated by. The amount of n-decane soluble component (the amount of soluble component
The smaller the composition distribution, the smaller the measurement).
g in 450 ml of n-decane, dissolve at 145 ° C, and
And remove the n-decane-insoluble part by filtration.
This is performed by recovering the n-decane soluble part. Thus, the differential scanning calorimeter (DSC)
Temperature at the maximum peak position in the endothermic curve measured
Relationship between (Tm) and density (d), and n-decane soluble
The quantity fraction (W) and the density (d) have the above relationship.
Ethylene-α-olefin copolymer (A)
It can be said that the composition distribution is narrow. Ethylene α-having the above-mentioned properties
The olefin copolymer (A) is, for example, an organic resin described later.
Luminium oxy compound (a), transition metal compound (b-
I), transition metal compound (b-II) and carrier, if necessary
Formed from organoaluminum compound (c)
In the presence of a fin polymerization catalyst, ethylene and C3
And α-olefin having a density of from 20 to 20
Is 0.850 to 0.980 g / cm^ThreeCo-weight to be
It can be manufactured by combining. [Ethylene / α-olefin copolymer
(B)] Forming the ethylene copolymer composition according to the present invention
Ethylene-α-olefin copolymer (B)
Land with olefin and α-olefin having 3 to 20 carbon atoms
Copolymer. Charcoal used for copolymerization with ethylene
Α-olefins having 3 to 20 elemental atoms include propylene
1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetra
Radecene, 1-hexadecene, 1-octadecene, 1-eico
And the like. Among them, 3 to 3 carbon atoms
Α-olefins of 10 are preferred, having 3 to 6 carbon atoms.
α-olefins are more preferred. Ethylene / α-olefin copolymer (B)
Then, the structural unit derived from ethylene is 50 to 100
% By weight, preferably 55-99% by weight, more preferably
65-98% by weight, most preferably 70-97% by weight
Α-olefin with 3-20 carbon atoms
The structural unit derived therefrom is 0 to 50% by weight, preferably 1 to 50% by weight.
45% by weight, more preferably 2-35% by weight, most preferably
Or 4 to 30% by weight.
No. Such ethylene / α-olefin copolymer
The union (B) has the following properties (i) and (ii).
It is preferred to have the following (i) to (vi)
It is more preferable to have such characteristics. (I) The density (d) is 0.850 to 0.9.
80g / cm^Three, Preferably 0.910 to 0.960 g
/ Cm^Three, More preferably 0.915 to 0.955 g /
cm^Three, Most preferably 0.920 to 0.950 g / c
m^ThreeIs desirably within the range. (Ii) The pole measured at 135 ° C. in decalin
The limiting viscosity [η] is 0.4 to 8 dl / g, preferably 0.4 to 8 dl / g.
1.25 dl / g, more preferably 0.5 to 1.23 dl /
It is desirably in the range of g. (Iii) According to a differential scanning calorimeter (DSC)
Temperature at the maximum peak position of the endothermic curve measured [Tm
(° C.)] and density [d (g / cm^Three)] Tm <400 × d-250 Preferably, Tm <450 × d-297 More preferably, Tm <500 × d-344. Particularly preferably, Tm <550 × d-391 It is desirable to satisfy the relationship shown by. (Iv) n-decane soluble component at room temperature
Rate [W (% by weight)] and density [d (g / cm^Three)] When MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9)^0.26× exp (−100 (d−
0.88)) + 0.1 Satisfies the relationship indicated by. Thus, the differential scanning calorimeter (DSC)
Temperature at the maximum peak position in the endothermic curve measured
Relationship between (Tm) and density (d), and n-decane soluble
The quantity fraction (W) and the density (d) have the above relationship.
Ethylene-α-olefin copolymer (B)
It can be said that the composition distribution is narrow. Ethylene α-having the above-mentioned properties
The olefin copolymer (B) may be an organic alcohol as described below.
Minium oxy compound (a), transition metal compound
(B '), and a carrier, if necessary, an organoaluminum
Existence of catalyst for olefin polymerization formed from compound (c)
In the presence, ethylene and α-olefins having 3 to 20 carbon atoms
And the density of the obtained copolymer is 0.850 to 0.9.
80g / cm^ThreeBy copolymerizing so that
Can be manufactured. Next, the ethylene copolymer composition of the present invention is
Ethylene-α-olefin copolymer (A)
Which is a catalyst component used in the copolymerization of (B) and (B)
Aluminum oxy compound (a), transition metal compound (b
-I), transition metal compound (b-II), cyclopentadienyl
Group IV transition metals containing ligands with a skeleton
Compound (b '), carrier and organoaluminum compound
(C) will be specifically described. In the present invention, ethylene / α-olefin
Used for copolymerization of copolymers (A) and (B)
Organic aluminum oxy compound (a) (hereinafter referred to as “component
(A) ". ) Is a conventionally known ben
It may be a zen-soluble aluminoxane.
A vent disclosed in Japanese Patent Application Laid-Open No. Hei 2-276807.
Even in the case of insoluble organoaluminum oxy compounds
Good. Conventionally known aluminoxanes include, for example,
It can be manufactured by the method as described above. (1) Contains a compound containing water of adsorption or water of crystallization
Salts, such as magnesium chloride hydrate, copper sulfate hydrate
Material, aluminum sulfate hydrate, nickel sulfate hydrate, salt
To a suspension of a hydrocarbon medium such as cerium iodide hydrate
Organoaluminum compounds such as lithium alkyl aluminum
To the adsorbed water or
A method of reacting with crystallization water. (2) Benzene, toluene, ethyl ether
Trialkyl in a medium such as
Water or organic aluminum compounds such as aluminum
A method of applying ice or water vapor. (3) Medium such as decane, benzene, and toluene
Organic aluminum such as trialkyl aluminum in the body
Compounds include dimethyltin oxide and dibutyltinoxy
A method of reacting an organic tin oxide such as oxide. The aluminoxane can be used in a small amount of organic
It may contain a metal component. In addition, the collected
Solvent or unreacted organic aluminum
After removing the compound by distillation,
Good. Used in preparing aluminoxane
As the organoaluminum compound, specifically, trimethyl
Aluminum, triethyl aluminum, tripropyl
Aluminum, triisopropyl aluminum, tri n-
Butyl aluminum, triisobutyl aluminum,
Sec-butyl aluminum, tri-tert-butyl aluminum
Aluminum, tripentyl aluminum, trihexyl aluminum
, Trioctyl aluminum, tridecyl aluminum
Trialkylaluminums such as aluminum;
Xyl aluminum, tricyclooctyl aluminum
Tricycloalkylaluminum; dimethylal
Minium chloride, diethylaluminum chloride, di
Ethyl aluminum bromide, diisobutyl aluminum
Dialkylaluminum halides such as muchloride;
Ethyl aluminum hydride, diisobutyl aluminum
Dialkylaluminum high such as aluminum hydride
Dride; dimethyl aluminum methoxide, diethyl
Dialkyl aluminum such as aluminum ethoxide
Alkoxide; diethylaluminum phenoxide, etc.
Dialkyl aluminum aryloxide and the like
It is. Of these, trialkyl aluminum
And tricycloalkylaluminum are particularly preferred
No. In addition, as this organoaluminum compound,
General formula (I-C_FourH₉)_xAl_y(C_FiveH_Ten)_z (X, y, z are positive numbers and z ≧ 2x)
Can be used
You. The above-mentioned organoaluminum compound is
Used alone or in combination. Aluminoxane
Solvents used during preparation include benzene and toluene.
Aromatic hydrocarbons such as butane, xylene, cumene, cymene,
Pentane, hexane, heptane, octane, decane, de
Aliphatic carbonization such as decane, hexadecane and octadecane
Hydrogen, cyclopentane, cyclohexane, cycloocta
Alicyclic hydrocarbons such as
Petroleum fractions such as phosphorus, kerosene, and light oil or the above aromatic coals
Halogenation of hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons
Substances, especially hydrocarbon solvents such as chlorinated products and brominated products.
No. In addition, ethyl ether, tetrahydrof
Ethers such as orchids can also be used. these
Among the solvents, aromatic hydrocarbons are particularly preferred. The benzene insoluble used in the present invention
Organic aluminum oxy compounds are converted to benzene at 60 ° C.
Al component to be dissolved is preferably 10% or less in terms of Al atom.
5% or less, particularly preferably 2% or less.
Insoluble or poorly soluble in Such an organic aluminum oxy compound
Has a solubility in benzene of 100 milligram atoms.
The organic aluminum oxy compound corresponding to Al
After suspending in 0 ml of benzene, stirring at 60 ° C for 6 hours
After mixing, filter the G-5 glass filter with jacket
Use, hot filtration at 60 ° C, separation on filter
The solid part thus obtained is washed four times with 50 ml of benzene at 60 ° C.
The amount of Al atoms present in all filtrates after washing (x
Mmol) (x%). In the present invention, ethylene / α-olefin
Transition metal compound used in copolymerization of copolymer (A)
The product (b-I) is specifically represented by the following formula [b-I]
A transition metal compound, and a transition metal compound (b-II)
Is a transition metal represented by the following formula [b-II]
Compound. ML¹ _X      … [B-I] (Where M is a transition metal source selected from Group IVB of the periodic table)
Child and L¹Is a ligand that coordinates to the transition metal atom M
And at least two of these ligands L¹Is a shik
Lopentadienyl group, methylcyclopentadienyl group,
An ethylcyclopentadienyl group or a carbon source
At least one selected from hydrocarbon groups having 3 to 10 carbon atoms
A substituted cyclopentadienyl group having the group
Exchange) ligand L other than cyclopentadienyl group¹Is carbon
C1-C12 hydrocarbon group, alkoxy group, arylo
Xy group, trialkylsilyl group, halogen atom or water
X is the valence of the transition metal atom M. ) ML^Two _X      … [B-II] (Where M is a transition metal source selected from Group IVB of the periodic table)
Indicates a child, L^TwoIs a ligand that coordinates to the transition metal atom.
And at least two of these ligands L^TwoReplace
Having a cyclopentadienyl skeleton which may have a group
These groups include hydrocarbon groups, silylene
Group or substituted silylene group,
Ligands other than ligands having a lopentadienyl skeleton L^Two
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
Aryloxy group, trialkylsilyl group, halogen atom
Or a hydrogen atom, and X represents the valence of the transition metal atom M.
Shown). Hereinafter, the transition represented by the above general formula [b-I]
The transfer metal compound (b-I) and the general formula [b-II]
More specific about the transition metal compound (b-II)
Will be explained. In the above formula [b-I], M is the first digit in the periodic table.
A transition metal atom selected from Group IVB, and specifically,
Zirconium, titanium or hafnium, preferred
Is zirconium. L¹Is a ligand coordinated to the transition metal atom M
And at least two of these ligands L¹Is
Cyclopentadienyl group, methylcyclopentadienyl
Group, ethylcyclopentadienyl group, or charcoal
At least one selected from hydrocarbon groups having 3 to 10 elementary atoms
A substituted cyclopentadienyl group having one kind of substituent
You. Each of these ligands may be the same or different.
You may. Also, other than (substituted) cyclopentadienyl groups
Ligand L¹Is a hydrocarbon group having 1 to 12 carbon atoms,
Coxy group, aryloxy group, halogen atom, trialkyl
It is a rusilyl group or a hydrogen atom. The substituted cyclopentadienyl group is substituted
It may have two or more groups, and two or more substituents are each
Each may be the same or different. Substituted cyclopenes
When a tadienyl group has two or more substituents,
A hydrocarbon group having at least one substituent having 3 to 10 carbon atoms
Other substituents may be methyl, ethyl or
Is a hydrocarbon group having 3 to 10 carbon atoms. As a hydrocarbon group having 3 to 10 carbon atoms,
Physically, alkyl group, cycloalkyl group, aryl
And aralkyl groups. More
Physically, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, t-butyl group, pliers
Hexyl group, octyl group, 2-ethylhexyl group,
Alkyl group such as decyl group; cyclopentyl group, cyclo
Cycloalkyl group such as hexyl group; phenyl group, tri
Aryl groups such as benzyl group; benzyl group, neophyl group, etc.
Can be exemplified. Of these, an alkyl group is preferred,
A ropyl group and an n-butyl group are particularly preferred. In the present invention,
(Substituted) cyclopentadienyl group coordinated to a transfer metal atom
Is preferably a substituted cyclopentadienyl group,
Cyclopentadi substituted by an alkyl group having 3 or more atoms
An enyl group is more preferred, and a disubstituted cyclopentadienyl
Group is more preferred, and a 1,3-substituted cyclopentadienyl group is
Particularly preferred. In the compound represented by the general formula [b-I],
A transition metal atom such as a compound represented by the general formula [b-II]
Two (substituted) cyclopentadienyl groups coordinated to M are
Not linked through a hydrocarbon group or the like. In the general formula [b-I], the transition gold
A (substituted) cyclopentadienyl group coordinated to a group atom M
Outer ligand L¹Is a hydrocarbon group having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, trialkylsilyl
Group, a halogen atom or a hydrogen atom. As a hydrocarbon group having 1 to 12 carbon atoms
Represents an alkyl group, a cycloalkyl group, an aryl group,
And the like, and more specifically,
Methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-butyl
Group, pentyl group, hexyl group, octyl group, 2-ethyl
Alkyl groups such as xyl and decyl groups; cyclopentyl
Groups, cycloalkyl groups such as cyclohexyl groups; phenyl
Aryl, tolyl, and other aryl groups; benzyl, neof
And an aralkyl group such as an aryl group. Examples of the alkoxy group include a methoxy group and an ethoxy group.
Xy, n-propoxy, isopropoxy, n-butoxy
Si, isobutoxy, sec-butoxy, t-butoxy
Group, pentoxy group, hexoxy group, octoxy group, etc.
Examples can be given. Examples of the aryloxy group include a phenoxy group.
And the like. Trialkylsilyl group
Trimethylsilyl, triethylsilyl,
Examples thereof include a phenylsilyl group. Halogen is fluorine, chlorine, bromine,
It is urine. The transition represented by such a general formula [b-I]
Bis (cyclopentadienyl) is used as the transfer metal compound.
Zirconium dichloride, bis (methylcyclopentadi
Enyl) zirconium dichloride, bis (ethylcyclo)
Pentadienyl) zirconium dichloride, bis (n-
Ropylcyclopentadienyl) zirconium dichloride
De, bis (n-butylcyclopentadienyl) zirconium
Mudichloride, bis (n-hexylcyclopentadienyl
Le) zirconium dichloride, bis (methyl-n-propyl
Rucyclopentadienyl) zirconium dichloride, bi
(Methyl-n-butylcyclopentadienyl) zirconi
Um dichloride, bis (dimethyl-n-butylcyclopen
Tadienyl) zirconium dichloride, bis (n-butyl)
Cyclopentadienyl) zirconium dibromide, bis
(N-butylcyclopentadienyl) zirconium methoxide
Cyclolide, bis (n-butylcyclopentadienyl) di
Ruconium ethoxycyclolide, bis (n-butylcyclope
Antadienyl) zirconium butoxycyclolide, bis
(N-Butylcyclopentadienyl) zirconium diethyl
Oxide, bis (n-butylcyclopentadienyl) zircon
Ium methyl chloride, bis (n-butylcyclopentadi
Enyl) zirconium dimethyl, bis (n-butylcyclo)
Pentadienyl) zirconium benzyl chloride, bis
(N-butylcyclopentadienyl) zirconium diben
Zir, bis (n-butylcyclopentadienyl) zirconi
Phenyl chloride, bis (n-butylcyclopentadi
Enyl) zirconium hydride chloride
Can be In the above example, cyclopentadienyl
Di-substituted ring includes 1,2- and 1,3-substituted, tri-substituted
The body includes 1,2,3- and 1,2,4-substituted forms. Also,
Zirconium compounds such as zirconium metal
Is replaced with titanium metal or hafnium metal
Metal compounds can be used. The transition represented by the general formula [b-I]
Among the metal transfer compounds, bis (n-propylcyclopen
Tadienyl) zirconium dichloride, bis (n-butyl)
Cyclopentadienyl) zirconium dichloride, bis
(1-methyl-3-n-propylcyclopentadienyl) zyl
Conium dichloride, bis (1-methyl-3-n-butylcyclyl)
Lopentadienyl) zirconium dichloride is particularly preferred.
Good. In the general formula [b-II], M is a periodic rule.
A transition metal atom selected from Group IVB of the Table, specifically
Is zirconium, titanium or hafnium, preferably
Preferable is zirconium. L^TwoIs a ligand that coordinates to the transition metal atom.
And at least two of these ligands L^TwoIs a shik
A ligand having a lopentadienyl skeleton.
Ligands having a lopentadienyl skeleton have a substituent
May be. Ligand having cyclopentadienyl skeleton
Specifically, for example, a cyclopentadienyl group,
Methylcyclopentadienyl group, dimethylcyclopenta
Dienyl group, trimethylcyclopentadienyl group, tet
Lamethylcyclopentadienyl group, pentamethylcyclo
Pentadienyl group, ethylcyclopentadienyl group,
Tyl ethyl cyclopentadienyl group, propyl cyclope
Antadienyl group, methylpropylcyclopentadienyl
Group, butylcyclopentadienyl group, methylbutylcyclyl
Lopentadienyl group, hexylcyclopentadienyl group
Alkyl-substituted cyclopentadienyl groups such as
Ndenyl group, 4,5,6,7-tetrahydroindenyl group, full
An enyl group and the like can be exemplified. These groups
Is a halogen atom, a trialkylsilyl group, etc.
It may be substituted. These cyclopentadienyl skeletons
Of the two ligands are hydrocarbon groups and silyl groups.
Linked through a silyl group or a substituted silylene group. Charcoal
Hydrogen groups include alkyl such as ethylene and propylene.
Such as len group, isopropylidene and diphenylmethylene
A substituted alkylene group;
Represents a dimethylsilylene group, a diphenylsilylene group,
And a ruphenylsilylene group. In the above formula [b-II], the transition metal
A structure having a cyclopentadienyl skeleton coordinated to an atom M
Ligands other than ligands L^TwoIs L in the above general formula [b-I]¹When
Similar hydrocarbon groups having 1 to 12 carbon atoms, alkoxy
Group, aryloxy group, trialkylsilyl group, halogen
Atom or hydrogen atom. This is represented by the general formula [b-II]
As the transition metal compound, ethylene bis (indenyl)
Dimethyl zirconium, ethylene bis (indenyl) di
Ethyl zirconium, ethylene bis (indenyl) diph
Enyl zirconium, ethylenebis (indenyl) methyl
Ruzirconium monochloride, ethylene bis (indeni
Le) Ethyl zirconium monochloride, ethylene bis
(Indenyl) methyl zirconium monobromide, ethyl
Lenbis (indenyl) zirconium dichloride, ethi
Lenbis (indenyl) zirconium dibromide, ethi
Lenbis {1- (4,5,6,7-tetrahydroindenyl)} di
Methyl zirconium, ethylene bis {1- (4,5,6,7-tet
Lahydroindenyl)｝ methylzirconium monochloride
, Ethylenebis ｛1- (4,5,6,7-tetrahydroindenyl
Le) zirconium dichloride, ethylene bis {1- (4,
5,6,7-tetrahydroindenyl) zirconium dibro
Mido, ethylenebis {1- (4-methylindenyl)} zyl
Conium dichloride, ethylene bis {1- (5-methylin
Denenyl) zirconium dichloride, ethylene bis
(6-methylindenyl) zirconium dichloride, d
Tylene bis {1- (7-methylindenyl)} zirconium
Dichloride, ethylenebis (1-methoxy-5-denidene)
Le) zirconium dichloride, ethylene bis {1- (2,
3-dimethylindenyl) zirconium dichloride, d
Tylene bis {1- (4,7-dimethylindenyl)} zirconi
Um dichloride, ethylenebis (1-, 4,7-dimethoxyyl)
Ndenyl) zirconium dichloride, isopropylide
(Cyclopentadienyl-fluorenyl) zirconium
Mudichloride, isopropylidene (cyclopentadienyl
2,7-di-t-butylfluorenyl) zirconium dichloride
Lido, isopropylidene (cyclopentadienyl-methyl
Lecyclopentadienyl) zirconium dichloride, di
Methylsilylene bis (cyclopentadienyl) zirconi
Um dichloride, dimethylsilylenebis (methylcyclo
Pentadienyl) zirconium dichloride, dimethyl
Rylene bis (dimethylcyclopentadienyl) zirconi
Um dichloride, dimethylsilylene bis (trimethyl
Clopentadienyl) zirconium dichloride, dimethi
Rusilylenebis (indenyl) zirconium dichloride
De, diphenylsilylene bis (indenyl) zirconium
Mudichloride and the like. In the above example,
The disubstituted cyclopentadienyl ring is 1,2- and 1,
Including 3-substituted, tri-substituted is 1,2,3- and 1,2,4-substituted
including. In the present invention, the zirconium compound as described above
Wherein zirconium metal is replaced with titanium metal or
It is possible to use transition metal compounds replaced with
it can. These are represented by the general formula [b-II]
Among the transition metal compounds, ethylene bis (indene
G) zirconium dichloride, dimethylsilylenebis
(Indenyl) zirconium dichloride, diphenyl
Rylene bis (indenyl) zirconium dichloride is special
Preferred. In the present invention, ethylene / α-olefin
In producing the polymer (A), the above-mentioned general formula [b-I]
At least one selected from the transition metal compounds represented
And a transition metal compound represented by the above general formula [b-II]
And at least one selected from them. Specifically, bis (1-methyl-3-n-butyl)
Cyclopentadienyl) zirconium dichloride and ethyl
Pair with Lenbis (indenyl) zirconium dichloride
Combination, bis (1-methyl-3-n-propylcyclopenta
Dienyl) zirconium dichloride and ethylene bis (a
Ndenyl) Combination with zirconium dichloride,
Sus (1-methyl-3-n-butylcyclopentadienyl) silyl
Conium dichloride and dimethylsilylene bis (indeni
B) Combination with zirconium dichloride, bis (1-
Methyl-3-n-butylcyclopentadienyl) zirconium
Mudichloride and diphenylsilylenebis (indenyl)
Combinations with zirconium dichloride are preferred. Transition metallation represented by the above general formula [b-I]
At least one transition metalation selected from compounds (b-I)
And a transition metal compound represented by the above general formula [b-II].
At least one transition metal compound selected from compounds (b-II)
The substance is 99/1 to 80/2 in a molar ratio (b-I / b-II).
0, preferably 97/3 to 82/18, more preferably
Used in such an amount as to be in the range of 95/5 to 85/15.
Is desirable. In such a ratio, the above general formula [b-
I] selected from the transition metal compounds (b-I)
At least one transition metal compound and the above-mentioned general formula [b-II]
Selected from transition metal compounds (b-II)
By using both one type of transition metal compound,
Excellent moldability, excellent optical properties and / or mechanical strength
Ethylene, which can form a modified ethylene copolymer composition
α-olefin copolymer (A) can be produced
You. The molar ratio (b-I / b-II) is in the range of 95/5 to 85/15.
When used in the amount specified, the optical properties and mechanical strength
Ethylene capable of forming an excellent ethylene copolymer composition
・ Can produce α-olefin copolymer (A)
You. Hereinafter, the term "component (b)" will be referred to as
Selected from transition metal compounds (b-I) represented by the formula [b-I]
And at least one kind represented by the above general formula [b-II]
At least one selected from transition metal compounds (b-II)
Transition metal compound catalyst component containing
You. In the present invention, ethylene / α-olefin
(B ') cycle used in copolymerization of copolymer (B)
Periodic table containing ligands having a lopentadienyl skeleton
Group IV transition metal compound (hereinafter referred to as “component (b ′)”)
Sometimes. ) Has a cyclopentadienyl skeleton
A transition metal compound belonging to Group IV of the periodic table containing a ligand
Is not particularly limited, but is represented by the following general formula [b-III].
Preferably, the transition metal compound is a transition metal compound. ML_x    ... [b-III] (Where M is a transition metal source selected from Group IVB of the periodic table)
L is a ligand that coordinates to the transition metal atom,
At least one L has a cyclopentadienyl skeleton
Ligands having a cyclopentadienyl skeleton
L other than the ligand is a hydrocarbon group having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, trialkylsilyl group,
SO_ThreeR group (where R has a substituent such as halogen)
A hydrocarbon group having 1 to 8 carbon atoms which may be present), halogen
X is the valence of a transition metal atom
It is. ) The transition metal compound represented by the general formula [b-III]
Is a transition metal compound represented by the above general formula [b-I] (b-
Transition metal compounds represented by I) and the above general formula [b-II]
(B-II). In the above general formula [b-III], M is a period
A transition metal atom selected from Group IVB of the
Is zirconium, titanium or hafnium,
Preferably, it is zirconium. Ligand having cyclopentadienyl skeleton
Are, for example, those exemplified in the above formula [b-II].
Similar ligands are mentioned. In the above general formula [b-III]
Coordination of Compounds Having a Cyclopentadienyl Skeleton
When two or more of the cyclopentenes
Ligands having a tadienyl skeleton are ethylene,
Alkylene groups such as pyrene, isopropylidene,
Substituted alkylene group such as nilmethylene, silylene group or
Is dimethylsilylene group, diphenylsilylene group, methyl
Through substituted silylene groups such as phenylsilylene groups
They may be combined. A ligand having a cyclopentadienyl skeleton
Specific examples of the ligand L other than
No. As a hydrocarbon group having 1 to 12 carbon atoms
Represents an alkyl group, a cycloalkyl group, an aryl group,
And more specifically an alkyl group.
Are methyl, ethyl, propyl, isopropyl
Pill group, butyl group and the like are exemplified, and cycloalkyl group and
Examples include cyclopentyl and cyclohexyl groups
And aryl groups such as phenyl and tolyl
Examples of the aralkyl group include a benzyl group and
An ophyl group is exemplified. As the alkoxy group, a methoxy group,
Examples include ethoxy and butoxy groups, and aryloxy.
Examples of the group include a phenoxy group and the like.
Examples include fluorine, chlorine, bromine, iodine, etc.
You. SO_ThreeAs the ligand represented by R, p-to
Ruensulfonato group, methanesulfonato group, trifluoro
And a methanesulfonato group. Such a system
Transition metal containing ligand having clopentadienyl skeleton
The compound is, for example, when the valence of the transition metal is 4,
More specifically, it is represented by the following general formula [b-III ']. R^Two _kR^Three _lR^Four _mR^Five _nM ... [b-III '] (Wherein M is the above transition metal atom, and R^TwoIs cyclope
A group (ligand) having an antadienyl skeleton;^Three,
R^FourAnd R^FiveIs a group having a cyclopentadienyl skeleton,
Alkyl group, cycloalkyl group, aryl group, aralkyl
Group, alkoxy group, aryloxy group, trialkyl
Ryl group, SO_ThreeR group, halogen atom or hydrogen atom
Where k is an integer of 1 or more, and k + 1 + m + n = 4.
You. ) In the present invention, in the above general formula, R^Two, R^Three, R^Fourand
R^Five(For example, R^TwoAnd R^Three) Is cyclopen
Metallocene which is a group (ligand) having a tadienyl skeleton
Compounds are preferably used. In this case, these
Groups having a clopentadienyl skeleton are ethylene, propylene
Alkylene groups such as len, isopropylidene, diphenyl
Substituted alkylene group such as rumethylene, silylene group or
Dimethylsilylene, diphenylsilylene, methylphenyl
Bonds through substituted silylene groups such as
It may be. Also, in this case, other ligands (for example,
R^FourAnd R^Five) Has a cyclopentadienyl skeleton
Group, alkyl group, cycloalkyl group, aryl group, ara
Alkyl, alkoxy, aryloxy, trialkyl
Lucyl group, SO_ThreeR, halogen or hydrogen
is there. Hereinafter, a transition metal in which M is zirconium
Specific examples of the compound are given below. Screw (in
(Denyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconi
Umbis (p-toluenesulfonato), bis (4,5,6,7-te
Trahydroindenyl) zirconium dichloride, bis
(Fluorenyl) zirconium dichloride, ethylene bi
(Indenyl) zirconium dichloride, ethylene bi
(Indenyl) zirconium dibromide, ethylene bi
(Indenyl) dimethyl zirconium, ethylene bis
(Indenyl) diphenyl zirconium, ethylene bis
(Indenyl) methyl zirconium monochloride, ethi
Lenbis (indenyl) zirconium bis (methanesul
Honato), ethylene bis (indenyl) zirconium bi
(P-toluenesulfonate), ethylene bis (indeni
Le) zirconium bis (trifluoromethanesulfona
G), ethylene bis (4,5,6,7-tetrahydroindenyl)
Le) zirconium dichloride, isopropylidene
Lopentadienyl-fluorenyl) zirconium dichloride
Lido, isopropylidene (cyclopentadienyl-methyl
Lecyclopentadienyl) zirconium dichloride, di
Methylsilylene bis (cyclopentadienyl) zirconi
Um dichloride, dimethylsilylenebis (methylcyclo
Pentadienyl) zirconium dichloride, dimethyl
Rylene bis (dimethylcyclopentadienyl) zirconi
Um dichloride, dimethylsilylene bis (trimethyl
Clopentadienyl) zirconium dichloride, dimethi
Rusilylenebis (indenyl) zirconium dichloride
Dimethylsilylenebis (indenyl) zirconium
Bis (trifluoromethanesulfonato), dimethylsilicone
Lenbis (4,5,6,7-tetrahydroindenyl) zirconi
Um dichloride, dimethylsilylene (cyclopentadie
Nyl-fluorenyl) zirconium dichloride, dife
Nylsilylene bis (indenyl) zirconium dichloride
, Methylphenylsilylenebis (indenyl) zirco
Dichloride, bis (cyclopentadienyl) silyl
Conium dichloride, bis (cyclopentadienyl) di
Ruconium dibromide, bis (cyclopentadienyl)
Methyl zirconium monochloride, bis (cyclopentane
Dienyl) ethyl zirconium monochloride, bis (Si
Clopentadienyl) cyclohexyl zirconium mono
Chloride, bis (cyclopentadienyl) phenylzyl
Conium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopen
Tadienyl) zirconium monochloride monohydric
De, bis (cyclopentadienyl) methyl zirconium
Monohydride, bis (cyclopentadienyl) dimension
Tylzirconium, bis (cyclopentadienyl) diph
Phenyl zirconium, bis (cyclopentadienyl) di
Benzyl zirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadi
Enyl) zirconium ethoxycyclolide, bis (cyclo
Pentadienyl) zirconium bis (methanesulfona
G), bis (cyclopentadienyl) zirconium bis
(P-toluenesulfonato), bis (cyclopentadienyl)
Le) zirconium bis (trifluoromethanesulfona
G), bis (methylcyclopentadienyl) zirconium
Mudichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopenta
Dienyl) zirconium ethoxycyclolide, bis (dim
Tylcyclopentadienyl) zirconium bis (trif
Fluoromethanesulfonato), bis (ethylcyclopentane)
Dienyl) zirconium dichloride, bis (methylethyl)
Rucyclopentadienyl) zirconium dichloride, bi
(Propylcyclopentadienyl) zirconium dik
Loride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadi
Enyl) zirconium dichloride, bis (methylbutyl)
Cyclopentadienyl) zirconium dichloride, bis
(Methylbutylcyclopentadienyl) zirconium bi
(Methanesulfonato), bis (trimethylcyclopen
Tadienyl) zirconium dichloride, bis (tetrame
Tylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium
Mudichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcycl
(Lopentadienyl) zirconium dichloride and the like. In the above example, cyclopentadie
Disubstituted nyl rings include 1,2- and 1,3-substituted,
Transformants include the 1,2,3- and 1,2,4-substituted. Prop
Alkyl groups such as n-, i-, sec-, tert-
And isomers. Further, the zirconium compound as described above
And replace zirconium with titanium or hafnium
The obtained compound can also be used. In the present invention,
Copolymer of the styrene-α-olefin copolymers (A) and (B)
The carrier used in the polymerization may be an inorganic or organic compound.
Having a particle size of 10 to 300 μm, preferably 20
Granular or fine-grained solids of up to 200 μm are used.
It is. Of these, porous oxides are preferred as inorganic carriers.
Specifically, SiO_Two, Al_TwoO_Three, MgO, ZrO_Two,
TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_Twoetc
Or mixtures thereof, such as SiO_Two-MgO, Si
O_Two-Al_TwoO _Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, S
iO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-Example of MgO
be able to. Of these, SiO_TwoAnd Al_TwoO_ThreeOr
At least one component selected from the group consisting of
Are preferred. The inorganic oxide contains a small amount of Na_TwoC
O_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoSO_Four,
Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)
_Two, Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonate such as O
May contain salts, sulfates, nitrates and oxides.
can not use. Such a carrier depends on its type and manufacturing method.
Although the properties are different, the carrier preferably used in the present invention
Has a specific surface area of 50 to 1000 m^Two/ G, preferably 1
00-700m^Two/ G and a pore volume of 0.3-2.
5cm^Three/ G is desirable. The carrier is required
100 to 1000 ° C., preferably 150 to 700
It is used by firing at ℃. In such a carrier, the amount of adsorbed water is 1.0
%, Preferably less than 0.5% by weight.
Preferably, the surface hydroxyl groups are at least 1.0% by weight, preferably
1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight
% By weight. Here, the amount of water adsorbed on the carrier (% by weight) and
The amount of surface hydroxyl groups (% by weight) is determined as follows.
You. [Amount of adsorbed water] at a temperature of 200 ° C. under normal pressure and nitrogen flow
Calculate the weight loss after drying for an hour, and calculate the weight before drying.
Is the amount of adsorbed water. [Amount of surface hydroxyl groups] At a temperature of 200 ° C under normal pressure and nitrogen flow
The weight of the carrier obtained by drying for 4 hours at X (g),
The carrier was further calcined at 1000 ° C. for 20 hours.
The weight of the fired product from which the surface hydroxyl groups have disappeared is defined as Y (g),
It is calculated by the following formula. [0088] Surface hydroxyl group content (% by weight) = {(XY) / X} × 100 Further, the carrier that can be used in the present invention includes granules
Granules or organic compounds having a diameter of 10 to 300 μm
Can be a particulate solid. These organic compounds
Products include ethylene, propylene, 1-butene, 4-methyl
Α-olefin having 2 to 14 carbon atoms, such as ru-1-pentene
(Co) polymer or vinyl
Produced mainly with rucyclohexane and styrene
A polymer or copolymer can be exemplified. In the present invention, the copolymer (A) is used for copolymerization.
The catalyst used is the above-mentioned organic aluminum oxy compound
(A), transition metal compound (b-I), transition metal compound (b
-II) and a copolymer (B) formed from a carrier
The catalyst used for the polymerization is an organoaluminum oxy compound.
(A), the transition metal compound (b '), and the carrier
But can be converted to organic aluminum if necessary.
Compound (c) may be contained. (C) Organic aluminum used as required
Compound (hereinafter sometimes referred to as “component (c)”).
You. ) Is represented, for example, by the following general formula [IV]
An organic aluminum compound can be illustrated. R¹ _nAlX_3-n  … [IV] (Where R¹Represents a hydrocarbon group having 1 to 12 carbon atoms.
X represents a halogen atom or a hydrogen atom, and n represents 1 to
3. ) In the above general formula [IV], R¹Is 1 to 12 carbon atoms
Hydrocarbon groups such as alkyl groups, cycloalkyl groups, etc.
Or an aryl group, specifically, a methyl group or an ethyl group.
Group, n-propyl group, isopropyl group, isobutyl group,
Pentyl group, hexyl group, octyl group, cyclopentyl
Group, cyclohexyl group, phenyl group, tolyl group, etc.
You. Such an organoaluminum compound (c)
Specific examples include the following compounds
You. Trimethyl aluminum, triethyl aluminum
System, triisopropylaluminum, triisobutyla
Luminium, trioctyl aluminum, tri-2-ethyl
Trialkyl aluminum such as hexyl aluminum
Alkenyl aluminum such as isoprenyl aluminum
Ium; dimethylaluminum chloride, diethylal
Minium chloride, diisopropyl aluminum chloride
, Diisobutylaluminum chloride, dimethylal
Dialkyl aluminum halide such as minium bromide
Do; methyl aluminum sesquichloride, ethyl aluminum
Sesquichloride, isopropyl aluminum
Cychloride, butyl aluminum sesquichloride, ethyl
Alkyl aluminum such as aluminum sesquibromide
Umsesquihalide; methyl aluminum dichloride,
Ethyl aluminum dichloride, isopropyl aluminum
Um dichloride, ethyl aluminum dibromide
Alkyl aluminum dihalide; diethyl aluminum
Hydride, diisobutyl aluminum hydride
Alkyl aluminum hydrides such as Further, the organic aluminum compound (c) is
Thus, a compound represented by the following general formula [V] may be used.
it can. R¹ _nAlY_3-n      … [V] (Where R¹Is the same as above, and Y is -OR^TwoGroup,-
OSiR^Three _ThreeGroup, -OAlR^Four _TwoGroup, -NR^Five _TwoGroup, -SiR
⁶ _ThreeGroup or -N (R⁷) AlR⁸ _TwoAnd n is 1 to 2
And R^Two, R^Three, R^FourAnd R⁸Is a methyl group, ethyl
Group, isopropyl group, isobutyl group, cyclohexyl
Group, phenyl group, etc.^FiveIs a hydrogen atom, methyl
Group, ethyl group, isopropyl group, phenyl group, trimethyl
A rusilyl group or the like;⁶And R⁷Is a methyl group, d
And a tyl group. ) Specific examples of such an organoaluminum compound include:
Include the following compounds. (1) R¹ _nAl (OR^Two)_3-nA compound represented by
For example, dimethyl aluminum methoxide, diethyl aluminum
Ethoxide, diisobutylaluminum methoxy
Such as (2) R¹ _nAl (OSiR^Three _Three)_3-nA compound represented by
For example, Et_TwoAl (OSiMe_Three), (Iso-Bu)_TwoA
l (OSiMe_Three), (Iso-Bu)_TwoAl (OSiE
t_Three)Such; (3) R¹ _nAl (OALR)^Four _Two)_3-nA compound represented by
For example, Et_TwoAlOAlEt_Two, (Iso-Bu)_TwoAlO
Al (iso-Bu)_TwoSuch; (4) R¹ _nAl (NR^Five _Two)_3-nA compound represented by
For example, Me_TwoAlNEt_Two, Et_TwoAlNHMe, Me_TwoAl
NHEt, Et_TwoAlN (SiMe_Three)_Two, (Iso-Bu)_Two
AlN (SiMe_Three)_Two  Such; (5) R¹ _nAl (SiR⁶ _Three)_3-nA compound represented by
For example (iso-Bu)_TwoAlSiMe_Three  Such; (6) R¹ _nAl (N (R⁷) AlR⁸ _Two)_3-nRepresented by
Compounds such as Et_TwoAlN (Me) AlEt_Two, (I
so-Bu)_TwoAlN (Et) Al (iso-Bu)_Two  Such. The compounds represented by the above general formulas [IV] and [V]
Among the organoaluminum compounds, the general formula R¹ _ThreeAl, R
¹ _nAl (OR^Two)_3-n, R¹ _nAl (OALR)^Four _Two)_3-nso
The compounds represented by the above formulas are preferred, and particularly, R is an isoalkyl group
And a compound wherein n = 2 is preferred. In the present invention, ethylene / α-olefin copolymerization
For olefin polymerization used in the production of isomer (A)
(A) includes component (a) and component (b) as described above.
And contacting the carrier and, if necessary, the component (c)
[Solid catalyst (A)] is preferably used.
Can be. Contacting components (a) to (c) with a carrier
The order in which they are performed is arbitrarily selected, but preferably the carrier and
The component (a) is mixed and brought into contact, and then the component (b) is mixed.
And, if necessary, further mixing component (c).
Let The component (b) is composed of two types forming the component (b).
After mixing the above transition metal compounds in advance, mix with other components
It is preferable to make contact. The above components (a) to (c) and the carrier
The contacting can be carried out in an inert hydrocarbon medium, the catalyst
Specific examples of the inert hydrocarbon medium used in the preparation of
Is propane, butane, pentane, hexane, hepta
Aliphatic charcoal such as octane, octane, decane, dodecane, kerosene
Hydrogen; cyclopentane, cyclohexane, methylcycl
Alicyclic hydrocarbons such as lopentane; benzene, tolue
Aromatic hydrocarbons such as ethylene and xylene; ethylene chloride
Halides such as chloride, chlorobenzene and dichloromethane
Such as hydrocarbons or mixtures thereof.
Wear. Component (a), component (b), carrier and necessary
When the component (c) is mixed and contacted according to
(B) is usually 5 × 10^-6~ 5 × 10^-FourMo
, Preferably 10^-Five~ 2 × 10^-FourUsed in molar amount
And the concentration of component (b) is about 10^-Four~ 2 × 10^-2Mol /
Liters (medium), preferably 2 × 10^-Four-10^-2Mole
/ Liter (medium). Aluminum of component (a)
Atom ratio of transition metal in component (b) (Al / transition
Metal transfer) is usually 10 to 500, preferably 20 to 20.
0. Aluminum of component (c) used as required
Aluminum atom (Al-c) and aluminum atom of component (a)
The atomic ratio (Al-c / Al-a) of (Al-a) is usually 0.02
-3, preferably 0.05-1.5. component
(A), component (b) and a carrier, optionally a component
The mixing temperature when mixing and contacting (c) is usually -50 to 1
50 ° C., preferably -20 to 120 ° C., contact time
Is from 1 minute to 50 hours, preferably from 10 minutes to 25 hours.
You. The solid catalyst (A) obtained as described above
[Solid catalyst component (A)] is converted into component (b) per 1 g of the carrier.
5 × 10 derived transition metal atoms^-6~ 5 × 10^-FourG
Atoms, preferably 10^-Five~ 2 × 10^-FourIn grams of atoms
Component (a) and component per gram of carrier supported
10 aluminum atoms derived from (c)^-3~ 5 × 10
^-2Gram atoms, preferably 2 × 10^-3~ 2 × 10^-2Gra
It is desirable that the metal is carried in the amount of the atom. The olefin polymerization catalyst (A) is as described above.
Component (a), component (b), carrier and if necessary
Prepolymerization of olefin in the presence of component (c)
Catalyst (preliminary polymerization catalyst (A)). Reserve
The polymerization is carried out using the components (a), (b),
Inert carbonization in the presence, if necessary, in the presence of component (c)
What to do by introducing olefins into a hydrogen medium
Can be. The components (a) and (b) and the carrier
Preferably, the solid catalyst component (A) is formed.
No. In this case, in addition to the solid catalyst component (A),
Component (a) and / or component not supported on the body
(C) may be added. The olefin used in the prepolymerization is
Of ethylene and α-ole having 3 to 20 carbon atoms
Fins, such as propylene, 1-butene, 1-pentene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-de
Examples of sen, 1-dodecene, 1-tetradecene, etc.
Can be. Of these, ethylene, or ethylene
And the α-olefin used in the polymerization.
Preferred. In the prepolymerization, the component (b) is
Usually 1 in terms of a transition metal atom derived from the component (b).
0^-6~ 2 × 10^-2Mol / l (vehicle), preferably
5 × 10^-Five-10^-2Used in moles / liter (medium)
Component (b) is usually 5 × 10^-6~ 5
× 10^-FourMole, preferably 10^-Five~ 2 × 10^-FourMolar amount
Used in. Aluminum of component (a) and component (b)
Has an atomic ratio (Al / transition metal) of usually 10
５００500, preferably 20-200. As needed
Atom (Al-c) of component (c) used for
Ratio of the aluminum atom (Al-a) to the component (a)
(Al-c / Al-a) is usually 0.02 to 3, preferably
It is in the range of 0.05 to 1.5. Prepolymerization temperature is -20
-80 ° C, preferably 0-60 ° C, and prepolymerization
Time is 0.5 to 100 hours, preferably about 1 to 50 hours
Degrees. The prepolymerized catalyst (A) is, for example,
It is prepared in this way. That is, the carrier is an inert hydrocarbon
To make a suspension. Then the organic aluminum was added to this suspension.
Moxy compound [component (a)] and react for a predetermined time
Let it. Thereafter, the supernatant is removed, and the resulting solid component is immiscible.
Resuspend with active hydrocarbons. Transition metal compound into this system
The product [component (b)] was added and reacted for a predetermined time.
The liquid is removed to obtain a solid catalyst component. Then organic aluminum
An inert hydrocarbon containing a compound (component (c))
Add the solid catalyst component obtained above and add olefin
To obtain a prepolymerized catalyst (A) by introducing
The olefin polymer produced by the polymerization is 0.1 g / g of the carrier.
1 to 500 g, preferably 0.2 to 300 g, more preferably
Preferably, the amount is 0.5 to 200 g. Ma
The prepolymerized catalyst (A) contains the component (b) per 1 g of the carrier.
Is about 5 × 10 as a transition metal atom^-6~ 5 × 10^-FourG
Atoms, preferably 10^-Five~ 2 × 10 ^-FourIn grams of atoms
Supported and derived from component (a) and component (c)
The minium atom (Al) is a transition metal derived from the component (b).
The molar ratio (Al / M) to the group atom (M) is 5 to 20.
0, preferably in the range of 10 to 150
Is desirable. The prepolymerization can be carried out either batchwise or continuously.
Can be performed under reduced pressure, normal pressure or increased pressure.
Any of the above can be performed. In the prepolymerization,
The pole measured in decalin at 135 ° C in the presence of hydrogen
The limiting viscosity [η] is in the range of 0.2 to 7 dl / g, preferably
Produce a prepolymer such that it is 0.5-5 dl / g
It is desirable. In the present invention, ethylene / α-olefin copolymer
For olefin polymerization used in the production of product (B)
(B) includes the above component (a), component
(B ') and a carrier, optionally component (c),
Catalyst (solid catalyst (B))
Can be. The solid catalyst (B) comprises the component (a), the component
Using (b ') and a carrier, if necessary, component (c)
It can be prepared in the same manner as the solid catalyst (A).
You. Solid catalyst (B) [Solid catalyst component (B)]
Is a transition metal atom derived from the component (b ') per gram of the carrier.
Is 5 × 10^-6~ 5 × 10^-FourGram atoms, preferably 10
^-Five~ 2 × 10^-FourSupported in the amount of gram atoms and the carrier 1
Aluminium derived from components (a) and (c) per g
10 atoms^-3~ 5 × 10^-2Gram atoms, preferably
2 × 10^-3~ 2 × 10^-2Carried in the amount of gram atoms
Is desirable. The olefin polymerization catalyst (B) is as described above.
Component (a), component (b '), carrier and if necessary
By pre-polymerizing the olefin in the presence of component (c)
Catalyst [preliminary polymerization catalyst (B)]. Forecast
The polymerization catalyst (B) is composed of the component (a), the component (b ′),
And a pre-polymerization catalyst using component (c) if necessary
It can be prepared in the same manner as in (A). The prepolymerized catalyst (B) is, for example,
It is prepared in this way. That is, the carrier is an inert hydrocarbon
To make a suspension. Then the organic aluminum was added to this suspension.
Moxy compound [component (a)] and react for a predetermined time
Let it. Thereafter, the supernatant is removed, and the resulting solid component is immiscible.
Resuspend with active hydrocarbons. Transition metal compound into this system
The product [component (b ')] was added and reacted for a predetermined time.
The supernatant is removed to obtain a solid catalyst component. Then organic aluminum
Hydrocarbon containing a sulfur compound [component (c)]
To the solid catalyst component obtained above,
To obtain a prepolymerized catalyst (B).
You. The olefin polymer produced by the prepolymerization is
0.1 to 500 g, preferably 0.2 to 3 per g of carrier
00 g, more preferably 0.5-200 g.
Is desirable. The prepolymerized catalyst (B) contains a carrier 1
The component (b ') per g is about 5 × 10^-6
~ 5 × 10^-FourGram atoms, preferably 10^-Five~ 2 × 10
^-FourComponent (a) and component (a) carried in the amount of gram atoms
The aluminum atom (Al) derived from (c) is a component
Molar ratio to transition metal atom (M) derived from (b ')
(Al / M), 5 to 200, preferably 10 to 150
Is desirably carried in an amount in the range described above. Forming the Ethylene Copolymer Composition of the Present Invention
Ethylene-α-olefin copolymer (A)
In the presence of an olefin polymerization catalyst (A), ethylene and
Α-olefins having 3 to 20 carbon atoms, such as
Pyrene, 1-butene, 1-pentene, 1-hexene, 4-methyl
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene, 1-d
It is obtained by copolymerizing with Icocene. The copolymerization of ethylene and α-olefin is as follows:
It is carried out in the gas phase or in the liquid phase in the form of a slurry. slurry
In the polymerization, an inert hydrocarbon may be used as a medium.
However, the olefin itself can be used as the medium. Inert carbon used in slurry polymerization
Specific examples of the hydrogen hydride medium include propane, butane, and isopropane.
Butane, pentane, hexane, octane, decane, dode
Aliphatic carbonization such as can, hexadecane and octadecane
Hydrogen; cyclopentane, methylcyclopentane, cyclo
Alicyclic hydrocarbons such as hexane and cyclooctane;
Aromatic hydrocarbons such as benzene, toluene and xylene;
Petroleum fractions such as gasoline, kerosene and light oil
You. Among these inert hydrocarbon media, aliphatic hydrocarbons
Preferred are hydrogen, alicyclic hydrocarbons, and petroleum fractions. The polymerization is carried out by a slurry polymerization method or a gas phase polymerization method.
When the olefin polymerization catalyst (A)
The concentration of transition metal atoms in^-8-10^-3G
Ram atoms / liter, preferably 10^-7-10^-FourG
Preferably, it is used in an amount of atoms / liter. In the polymerization, the carrier is supported on a carrier.
Organic aluminum oxy compound [component (a)] and
In addition to the aluminum compound [component (c)],
An unsupported organoaluminum oxy compound and
And / or an organoaluminum compound may be used. this
In some cases, unsupported organoaluminum oxy compound
And / or aluminum derived from organoaluminum compounds
Derived from minium atom (Al) and transition metal compound (b)
The atomic ratio (Al / M) to the transition metal atom (M) is 5
~ 300, preferably 10-200, more preferably 1
It is in the range of 5-150. When performing the slurry polymerization method, the polymerization temperature
The degree is usually -50 to 100 ° C, preferably 0 to 90 ° C.
Range, and when performing the gas phase polymerization method, the polymerization temperature
Is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.
It is an enclosure. The polymerization pressure is usually from normal pressure to 100 kg /
cm^Two, Preferably 2 to 50 kg / cm^TwoUnder pressurized condition
Yes, polymerization can be batch, semi-continuous, or continuous
It can also be done in an equation. Forming the Ethylene Copolymer Composition of the Present Invention
Ethylene-α-olefin copolymer (B)
In the presence of an olefin polymerization catalyst (B), ethylene and
Copolymerizes with α-olefin having 3 to 20 carbon atoms
Obtained by: Α-ole having 3 to 30 carbon atoms
Examples of the fin include the same as described above. The copolymerization of ethylene and α-olefin is as follows:
It is carried out in the gas phase or in the liquid phase in the form of a slurry. slurry
In the polymerization, an inert hydrocarbon may be used as a medium.
However, the olefin itself can be used as the medium. Inert carbon used in slurry polymerization
Examples of the hydrogen hydride medium include the same as described above.
Among these inert hydrocarbon media, aliphatic hydrocarbons and fats
Preferred are cyclic hydrocarbons and petroleum fractions. It is carried out by a slurry polymerization method or a gas phase polymerization method.
When the olefin polymerization catalyst (B) is used, the polymerization reaction system
The concentration of transition metal atoms in^-8-10^-3G
Ram atoms / liter, preferably 10^-7-10^-FourG
Preferably, it is used in an amount of atoms / liter. In the polymerization, the carrier is supported on a carrier.
Organic aluminum oxy compound [component (a)] and
In addition to the aluminum compound [component (c)],
An unsupported organoaluminum oxy compound and
And / or an organoaluminum compound may be used. this
In some cases, unsupported organoaluminum oxy compound
And / or aluminum derived from organoaluminum compounds
Minium atom (Al) and transition metal compound (b ')
The atomic ratio (Al / M) with the incoming transition metal atom (M) is
5-300, preferably 10-200, more preferably
It is in the range of 15 to 150. When performing the slurry polymerization method, the polymerization temperature
The degree is usually -50 to 100 ° C, preferably 0 to 90 ° C.
Range, and when performing the gas phase polymerization method, the polymerization temperature
Is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.
It is an enclosure. The polymerization pressure is usually from normal pressure to 100 kg /
cm^Two, Preferably 2 to 50 kg / cm^TwoUnder pressurized condition
Yes, polymerization can be batch, semi-continuous, or continuous
It can also be done in an equation. [Ethylene / α-olefin copolymer composition]
Product] to form the ethylene copolymer composition according to the present invention
The ethylene / α-olefin copolymer composition (I)
The ethylene / α-olefin copolymer (A) and ethylene
Ethylene-α-olefin copolymer (B)
Α-olefin copolymer (A) is 20-90 weight
%, Preferably 40 to 75% by weight.
Len-α-olefin copolymer (B) is 10 to 80 weight
%, Preferably 25 to 60% by weight
Is desirable. (However, ethylene / α-olefin copolymer
Combined (A) and ethylene / α-olefin copolymer (B)
Is not the same as Ethylene / α-olefin copolymers (A) and (B)
Is the density of the ethylene / α-olefin copolymer (A)
And the density of the ethylene / α-olefin copolymer (B)
Is preferably less than 1, more preferably (A / B).
Or 0.930 to 0.999
Used. Such ethylene / α-olefin copolymers
The combined composition (I) is as shown in the following (i) to (vi)
Preferably, it has properties. (I) Density is 0.850 to 0.980 g / cm^Three, Preferred
Or 0.890-0.955 g / cm^Three, More preferred
0.900 to 0.950 g / cm^ThreeThe range of
Is desirable. (Ii) At 190 ° C. under a load of 2.16 kg
The composition has a melt flow rate (MFR) of 0.1 to
100 g / 10 min, preferably in the range of 0.2 to 50 g / 10 min
It is desirable that it is an enclosure. (Iii) Melt tension at 190 ° C.
[MT (g)] and melt flow rate [MFR (g /
10 minutes)] MT ≧ 2.2 × MFR^-0.84 It is desirable to satisfy the relationship shown by. (Iv) The stress at 190 ° C. is 2.4 × 1
0⁶dyne / cm^TwoIs defined by the shear rate when reaching
Flow index [FI (1 / second)] and melt flow rate
And [MFR (g / 10 min)] FI> 100 × MFR Preferably FI> 130 × MFR More preferably, FI> 150 × MFR It is desirable to satisfy the relationship shown by. (V) By differential scanning calorimeter (DSC)
Temperature at maximum peak position of measured endothermic curve [Tm
(° C.)] and density [d (g / cm^Three)] Tm <400 × d-250 Preferably, Tm <450 × d-297 More preferably, Tm <500 × d-344. Particularly preferably, Tm <550 × d-391 It is desirable to satisfy the relationship shown by. (Vi) Amount of n-decane soluble component at room temperature
Fraction [W (% by weight)] and density [d (g / cm^Three)〕When
But, When MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9)^0.26× exp (−100 (d−
0.88)) + 0.1 It is desirable to satisfy the relationship shown by. Ethylene / α-olefin copolymer composition
(I) can be produced using a known method,
For example, it can be manufactured by the following method. (1) Ethylene / α-olefin copolymer (A)
Tylene / α-olefin copolymer (B) and optionally
Other components to be added, using an extruder, kneader, etc.
Method of mechanical blending. (2) Ethylene / α-olefin copolymer
(A) and an ethylene / α-olefin copolymer (B),
And other components to be added as required
For example; hexane, heptane, decane, cyclohexa
Hydrocarbons such as toluene, benzene, toluene and xylene
Solvent) and then removing the solvent. (3) Ethylene / α-olefin copolymer
(A) and an ethylene / α-olefin copolymer (B),
And other components added as needed in a suitable good solvent.
Mix and then prepare separately dissolved solutions, then
How to remove the solvent. (4) Combination of the above methods (1) to (3)
How to do it. Further, an ethylene / α-olefin copolymer composition
(I) uses one or a plurality of polymerization vessels to carry out copolymerization.
Separation into two or more stages with different reaction conditions
Lefin copolymer (A) and ethylene-α-olefin
Produced by copolymerizing the copolymer (B)
Can be used, and using multiple
And ethylene-α-olefin copolymer (A) and ethylene
Copolymerizing the len / α-olefin copolymer (B)
Can also be produced. [High pressure radical method low density polyethylene (I
I)] Next, the high pressure radical method low density po
The ethylene will be specifically described. High pressure radical method low density used in the present invention
Polyethylene is manufactured by so-called high-pressure radical polymerization
Polyethylene with many long-chain branches
190 ° C, 2.16k according to ASTM D1238-65T
The MFR measured under the condition of g load is 0.01 to 100.
g / 10 min, preferably 0.05 to 10 g / 10 min, more preferably
More preferably, it is in the range of 0.1 to 8 g / 10 min.
New In addition, high density radical method low density polyethylene
Has a density (d) of 0.910 to 0.930 g / cm^Threeof
It is desirable to be within the range. Density at 190 ° C
2.Measurement of melt flow rate (MFR) under 16kg load
Heat the strand obtained at the specified time at 120 ° C for 1 hour
After slowly cooling to room temperature over 1 hour, measure with density gradient tube
Is done. Further, the high-density radical method low-density polyethylene
Is the swell ratio that indicates the degree of long chain branching,
Inside diameter at 190 ° C using a fine flow property tester
(D) Extrusion speed from a nozzle of 2.0 mm and length of 15 mm
The diameter (Ds) of the strand extruded at 10 mm / min,
The ratio (Ds / D) to the nozzle inner diameter D is 1.3 or more.
Is desirable. The high-pressure radical method low-density polyethylene
Is other α- as long as the object of the present invention is not impaired.
Polymerization of olefin, vinyl acetate, acrylate, etc.
It may be a copolymer with a hydrophilic monomer. [Ethylene-based copolymer composition]
Ethylene-based copolymer composition,
Lefin copolymer composition (I) and high pressure radical method
Polyethylene (II), ethylene-α-ole
Fin copolymer composition (I), high pressure radical method low density
The weight ratio [(I) :( II)] to polyethylene (II) is 9
It is preferably in the range of 9: 1 to 60:40.
Is preferably in the range of 98: 2 to 70:30, especially
Preferably it is in the range of 98: 2 to 80:20.
Good. The high pressure radical method low density poly is higher than the above range.
If ethylene is low, the effect of improving transparency, melt tension, etc.
It may be insufficient, and if it is more than the above range, tensile
Strength, stress crack resistance, etc. can be significantly reduced
is there. The ethylene copolymer composition of the present invention includes:
As long as the object of the present invention is not impaired, a weather-resistant stabilizer, heat-resistant
Stabilizer, antistatic agent, antislip agent, antiblock
Agent, antifogging agent, lubricant, pigment, dye, nucleating agent, plasticizer, aged
Additives such as antioxidants, hydrochloric acid absorbents, and antioxidants are required
It may be blended accordingly. The ethylene-based copolymer composition of the present invention is
Can be manufactured using known methods, for example,
It can be manufactured by the method as described above. (1) Ethylene / α-olefin copolymer composition (I)
And high pressure radical method low density polyethylene (II), and
The other components that are added as desired can be added to an extruder, kneader, etc.
Method of mechanically blending using (2) Ethylene / α-olefin copolymer
Composition (I) and high-pressure radical method low-density polyethylene
(II) and other components added as required
Solvents (eg; hexane, heptane, decane, cyclo
Carbonization of hexane, benzene, toluene and xylene
A hydrogen solvent) and then removing the solvent. (3) Ethylene / α-olefin copolymer
Composition (I) and high-pressure radical method low-density polyethylene
(II) and other components added as required
Mix and prepare solutions separately dissolved in solvent
And then removing the solvent. (4) Combination of the above methods (1) to (3)
How to do it. The ethylene-based copolymer composition of the present invention can be used for ordinary air-cooled
Flation molding, air-cooled two-stage cooling inflation
Shape, high-speed inflation molding, T-die film forming
Shape, water-cooled inflation molding, etc.
Thus, a film can be obtained. Molding in this way
The resulting film has optical properties and / or mechanical strength
Heat sealing, which is a feature of ordinary LLDPE
Properties, hot tack properties, heat resistance, etc. Also,
Tylene / α-olefin copolymer (A) and (B)
The composition distribution is extremely narrow, so the film surface is sticky
Absent. In addition, the melt tension is high,
Excellent bubble stability during molding. Processing the ethylene copolymer composition of the present invention
The film obtained by performing
Film, lami web, sugar bag, oil bag, water bag
Various packaging films for packaging, food packaging, etc.
And agricultural materials. Also, nylon, poly
Laminated with a base material such as ester to form a multilayer film
It can also be used. Blow infusion bag, blow
Bottles, extruded tubes, pipes, tears
Injection molded products such as caps and daily necessities, fibers, rotational molding
It can also be used for large molded products. [0148] As described above, the ethylene copolymer composition of the present invention comprises:
An organoaluminum oxy compound and at least two features
And a transition metal compound.
Thiene / α-olefin copolymer (A) and organic alcohol
For catalysts containing minium oxy compounds and transition metal compounds
-Α-olefin copolymer that can be produced from
Ethylene / α-olefin copolymer composition comprising (B)
And low-density polyethylene by high-pressure radical method
Since it is formed, it has excellent moldability. Such an d
From the Tylene copolymer composition, haze, gloss, etc.
Machines such as optical properties and / or film impact
A film having excellent mechanical strength can be produced. [0149] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these examples.
Not. In the present invention, evaluation of physical properties of the film
Was performed as follows. [Haze (Haze)] Measured according to ASTM-D-1003-61
Was. [Gloss] According to JIS Z8741
Therefore it was measured. [Film Impact] Pendulum fill made by Toyo Seiki Seisakusho
With a film impact tester (film impact tester)
Specified. [0152] [Production Example 1]Polymerization of ethylene / 1-hexene copolymer [Preparation of catalyst component] Silica dried at 250 ° C. for 10 hours
5.0 kg were suspended with 80 liters of toluene
Then, it was cooled to 0 ° C. Then, methylaluminoxane
Solution of toluene (Al; 1.33 mol / l) 2
8.7 liters were added dropwise over one hour. At this time, the temperature inside the system
The temperature was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes.
The temperature was raised to 95 ° C over 1.5 hours,
Allowed to react for hours. Thereafter, the temperature was lowered to 60 ° C, and the supernatant was decanted.
It was removed by the notation method. The solid component obtained in this manner is
After washing twice with toluene, resuspend with 80 liters of toluene
did. Bis (1,3-n-butylmethylcyclopentene)
Tadienyl) zirconium dichloride in toluene
(Zr; 34.0 mmol / l) 7.4 liters
And ethylene bis (indenyl) zirconium dichloride
Lido toluene solution (Zr; 1.92 mmol / litre)
1) 14.6 liters are dropped at 80 ° C over 30 minutes
Then, the reaction was further performed at 80 ° C. for 2 hours. Then, the supernatant is
Removed and washed twice with hexane to remove
A solid catalyst containing 3.4 mg of zirconium was obtained. [Preparation of Preliminary Polymerization Catalyst]
85 liter hex containing isobutylaluminum
Sun was charged with 0.85 kg of the solid catalyst obtained above and 1-
76.5 g of hexene was added, and ethylene was added at 35 ° C. for 2 hours.
By performing the pre-polymerization, 3 g of po
A prepolymerized catalyst in which ethylene was prepolymerized was obtained. [Polymerization] Using a continuous fluidized bed gas phase polymerization apparatus
No, total pressure 20kg / cm^Two-G, Etch at 70 ° C polymerization temperature
Copolymerization of len and 1-hexene was performed. Prepared above
0.16 mmoles of zirconium atom converted from the prepolymerized catalyst
/ H, 10 mmol of triisobutylaluminum /
h and continuously supply a constant gas composition during the polymerization.
Ethylene, 1-hexene, hydrogen and nitrogen to maintain
Continuously supplied (gas composition; 1-hexene / ethylene =
0.030, hydrogen / ethylene = 4.3 × 10^-Four, Echire
Concentration = 25%). The thus obtained ethylene-1-hexene
The yield of the styrene copolymer (A-1) was 6.2 kg / h.
MFR is 0.44 g / 10 min and density is 0.91
5g / cm^ThreeAnd the decane-soluble portion at room temperature is 0.1.
It was 45% by weight. [0157] Example 1 The ethylene • 1-
Hexene copolymer (A-1)
Ethylene / 1-hexene polymerized in the same manner except for the
Copolymer (B-1) in a weight ratio of (A-1) / (B-1)
= 60/40 melt-kneaded to ethylene / α-olefin
Thus, a copolymer composition (L-1) was obtained. Ethylene 1-hex
Table 1 shows the physical properties of the ethylene copolymer (B-1).
Table 2 shows the physical properties of the α-olefin copolymer composition (L-1).
Shown in Ethylene / α-olefin copolymer composition
(L-1) and the high-density radical method
Mixing ratio of ethylene (H-1) (L-1 / H-1) = 9
0/10 dry blended and 100 parts by weight of resin
Against tri (2,4-di-t-butyl) as a secondary antioxidant
Ruphenyl) phosphate, 0.05 parts by weight, heat resistant
N-octadecyl-3- (4'-hydroxy-3 ', 5'
0.1 weight of (-di-t-butylphenyl) propionate
Parts, 0.1% calcium stearate as a hydrochloric acid absorbent.
05 parts by weight. After a while, Haike conical chart
Using a twin-screw extruder, knead at a set temperature of 180 ° C.
Thus, an ethylene copolymer composition was obtained. Ethylene copolymer composition obtained above
And a single screw extruder of 20 mmφ · L / D = 26, 25
mmφ die, lip width 0.7mm, single slit air
Using a ring, air flow rate = 90 l / min, extrusion rate =
9 g / min, blow ratio = 1.8, take-off speed = 2.4 m
/ Min, at a processing temperature of 200 ° C, a 30 μm thick
The film was blown. The melt properties and properties of the ethylene copolymer composition
Table 4 shows the physical properties of the film. Formability (MT), high shear
Excellent fluidity (FI) in the region, optical properties, film
A blown film with excellent impact is obtained
Was. [0161] Reference Example 1 Ethylene / α-olefin obtained in Example 1
The same as Example 1 except for using the vinyl copolymer composition (L-1).
30μm thick by inflation molding
The film was molded. Melt of ethylene copolymer composition
The properties and film properties are shown in Table 4. From Example 1 and Reference Example 1, Example 1
Blending high density radical method low density polyethylene
Improves the moldability (MT) and the optical properties of the film.
You can see that it was done. [0163] Comparative Example 1 Zirconi in the catalyst component in Production Example 1
Bis (1,3-n-butylmethylcyclope)
(Antadenyl) zirconium dichloride only
As in Production Example 1 except that the composition of the mixed gas
· 1-hexene copolymer (A-2) obtained by
And (B-2) by weight ratio (A-2) / (B-2) = 6
0/40 melt kneading and ethylene / α-olefin copolymer
A united composition (L-2) was obtained. Ethylene / α-olefin
Table 2 shows the physical properties of the copolymer composition (L-2). Ethylene / α-olefin copolymer composition
(L-2) and a low-density high-pressure radical method shown in Table 3.
Mixing ratio of ethylene (H-1) (L-2 / H-1) = 9
0/10 dry blend and melt blend as in Example 1.
By kneading, an ethylene-based copolymer composition was obtained. Using this ethylene copolymer composition,
Thickness by inflation molding in the same manner as in Example 1.
A 30 μm film was formed. Ethylene copolymer group
Table 4 shows the melt properties and film properties of the product. [0166] Comparative Example 2 Ethylene / α-olefin obtained in Comparative Example 1
The same as Example 1 except for using the vinyl copolymer composition (L-2).
30μm thick by inflation molding
The film was molded. Melt of ethylene copolymer composition
The properties and film properties are shown in Table 4. Example 1, Reference Example 1, and Comparative Examples 1 and 2
In Example 1, high-pressure radical method low-density polyethylene was used.
Great improvement in moldability (MT) by blending
I understand. [0168] Comparative Example 3 Zirconi in the catalyst component in Production Example 1
Except for changing the mixing ratio of the compound as shown in Table 1.
Ethylene / 1-hexene copolymer obtained in the same manner as in Example 1.
Combined (A-3) and ethylene / 1-hexene copolymer
The weight ratio of (B-3) is (A-3) / (B-3) = 60/4.
Melt-kneaded at 0, ethylene-α-olefin copolymer set
A product (L-3) was obtained. Ethylene / α-olefin copolymer
Table 2 shows the physical properties of the combined composition (L-3). Ethylene / α-olefin copolymer composition
(L-3) and the high-pressure radical method low-density polymer shown in Table 3.
Mixing ratio of ethylene (H-1) (L-3 / H-1) = 9
0/10 dry blend and melt blend as in Example 1.
By kneading, an ethylene-based copolymer composition was obtained. This
As in Example 1 using the ethylene copolymer composition of
Into a 30 μm thick filter by inflation molding.
Lum was molded. Melt properties of ethylene copolymer composition
Table 4 shows the physical properties of the film. [0170] Comparative Example 4 Ethylene / α-olefin obtained in Example 2
The same as Example 1 except for using the vinyl copolymer composition (L-3).
30μm thick by inflation molding
The film was molded. Melt of ethylene copolymer composition
The properties and film properties are shown in Table 4. [0171] Comparative Example 3 was more inflationary than the Example.
Poor transparency. [0172] Example 2 The ethylene / 1-hexene obtained in Production Example 1 above
A styrene copolymer (A-1) and the ethylene / 1-hexene
Weight ratio of copolymer (B-2) (A-1) / (B-2) =
Melt kneading at 70/30 and ethylene / α-olefin
A polymer composition (L-4) was obtained. Ethylene / α-olef
Table 2 shows the physical properties of the vinyl copolymer composition (L-4). Ethylene / α-olefin copolymer composition
Ethylene / α-olefin copolymer instead of (L-1)
Same as Example 1 except that body composition (L-4) was used.
Thus, an ethylene copolymer composition was obtained. This ethylene type
Inflation was performed in the same manner as in Example 1 using the polymer composition.
Forming a 30μm thick film
Was. Melt properties and fill of ethylene-based copolymer composition
Table 4 shows the physical properties. Moldability (MT), fluidity in high shear range
Excellent in (FI), excellent in optical properties and film impact
A blown film was obtained. [0175] [Reference Example 2] The ethylene / α-olefin obtained in Comparative Example 3
The same as Example 1 except for using the vinyl copolymer composition (L-4).
30μm thick by inflation molding
The film was molded. Melt of ethylene copolymer composition
The properties and film properties are shown in Table 4. From Example 2 and Reference Example 2, Example 2
Blending high density radical method low density polyethylene
Improves the moldability (MT) and the optical properties of the film.
You can see that it was done. [0177] [Table 1][0178] [Table 2] [0179] [Table 3] [0180] [Table 4]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akira Todo 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-6-136193 (JP, A) JP-A-4-213305 (JP, A) JP-A-3-203904 (JP, A) JP-A-4-213309 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08L 23/00-23/36 C08F 4/64-4/69 C08F 10/00-10/14

Claims (1)

(57) Claims: (I) At least one selected from (a) an organic aluminum oxy compound and (b-I) a transition metal compound represented by the following general formula [b-I] ML ¹ _X ... [b-I] (wherein M represents a transition metal atom selected from Group IVB of the periodic table, and L ¹ is a ligand coordinated to the transition metal atom M) Wherein at least two of the ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
An ethylcyclopentadienyl group or a substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups 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) at least one compound selected from transition metal compounds represented by the following general formula [b-II]: ML ² _X ... [b-II] (wherein M is Represents a transition metal atom selected from Group IVB, wherein L ² is a ligand coordinated to the transition metal atom, and at least two of the ligands L ² may have a substituent Ligand having cyclopentadienyl skeleton There, these groups, hydrocarbon groups are bonded via a silylene group or substituted silylene group, the ligand 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, a halogen atom or a hydrogen atom, and X represents the valency of the transition metal atom M.) The moles of the transition metal compound (b-I) and the transition metal compound (b-II) The ratio [(b-I) / (b-II)] is 99
/ 1 to 80/20 by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst having a density of 0.850 to 0/20. in the range of ^{.980g / cm 3, (ii)} 135 ℃, intrinsic viscosity measured in decalin at [eta]
(Iii) a melt tension at 190 ° C. [MT
(G)] and melt flow rate [MFR (g / 10 min)]
^Satisfies the relationship expressed by MT> 2.2 × MFR- ^0.84 , 20 to 90% by weight of an ethylene / α-olefin copolymer (A), (a) an organoaluminum oxy compound, and (b ′) cyclopentadiene. Obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound belonging to Group IV of the periodic table containing a ligand having an enyl skeleton. (I) the density is in the range of 0.850 to 0.980 g / cm ³ , (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
Of the ethylene / α-olefin copolymer (B) in the range of 0.4 to 8 dl / g (wherein ethylene / α-olefin copolymer The polymer (A) and the ethylene / α-olefin copolymer (B) are not the same); and (II) a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg of 0.01 to 100 g / 10 And a weight ratio of the (I) ethylene / α-olefin copolymer composition to the (II) low-density polyethylene [(I) :( II )] Is in the range of 99: 1 to 60:40.