JP3365661B2 - 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.
More specifically, a conventionally known ethylene copolymer
Transparency compared to coalesced or ethylene-based copolymer compositions
Film with excellent moldability and excellent moldability.
Have good adhesion to highly polar materials.
It relates to a polymer composition. [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 LUM at high speed,
For stable high-speed molding without cracking
Is a melt-based polymer for its molecular weight as an ethylene copolymer.
Must select a material with a large solution (melt tension).
No. A similar property is sag or
To prevent tearing or in T-die molding
Necessary to minimize width drop. In addition to this
In such extrusion molding, high shear rate during extrusion is required.
Stress of the ethylene copolymer during molding
Necessary from economic aspects such as quality improvement and power consumption reduction during molding
It is. [0003] Ziegler type catalysts, especially titanium-based catalysts
Melt Tension of Ethylene Polymer Obtained Using Catalyst
(Melt tension) and expansion ratio (die-well ratio)
Japanese Patent Application Laid-Open No. 56-90810 discloses a method for improving the moldability.
Or Japanese Patent Application Laid-Open No. 60-106806.
Proposed. However, it is generally obtained using a titanium catalyst.
Ethylene polymers, especially low-density ethylene copolymers
The body has a wide composition distribution, and molded bodies such as films are solid.
There was a problem that there was. [0004] Further, it is produced using a Ziegler type catalyst.
Of ethene-based polymers using chromium-based catalysts
The resulting ethylene-based polymer has a relatively high melt tension.
High, but has the disadvantage of poor thermal stability. This is
Chain ends of ethylene polymers produced using rom-based catalysts
It is considered that the ends are likely to be unsaturated bonds. [0005] Among 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, for example,
JP-A-60-35007 discloses cyclopentadienyl
Catalyzes zirconocene compounds containing thiol derivatives as ligands
Ethylene polymer obtained by using as
It is described that the compound contains one terminal unsaturated bond.
As with ethylene-based polymers obtained using ROM-based catalysts,
Poor stability is expected. Also, the molecular weight distribution is narrow.
It is feared that the fluidity during extrusion molding is poor.
You. [0006] Ethylene copolymers are generally
Since it has no polar group inside and is inherently non-polar,
Adhesion to highly polar materials such as metals or polar resins
Insufficiency. Therefore, it is bonded to highly polar material
When used together, the surface of the ethylene copolymer
No flame treatment, corona discharge treatment, or primer treatment
Must be performed, which complicates the operation.
You. For this reason, if the melt tension is high,
Small stress in high shear area, good thermal stability,
Excellent mechanical strength and good adhesion to highly polar materials
If a good ethylene-based copolymer composition emerges,
The target value is extremely large. [0008] SUMMARY OF THE INVENTION The present invention has been made in view of the above situation.
It has excellent moldability, excellent transparency,
Manufacture film with good adhesion to high polar materials
To provide an ethylene-based copolymer composition that can be used
It is an object. [0009] SUMMARY OF THE INVENTION The ethylene copolymer composition according to the present invention
Is [I] (a) an organoaluminum oxy compound, and (b)
Periodic law involving ligands with cyclopentadienyl skeleton
Table IV Group transition metal compound, for olefin polymerization
Ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a catalyst
(A-i) obtained by copolymerizing
0.850-0.980 g / cm^ThreeRange (A-
ii) The intrinsic viscosity [η] measured in decalin at 135 ° C. is
Ethylene / α-olefin in the range of 0.4 to 8 dl / g
20 to 90% by weight of the copolymer [A] and (a) an organic aluminum
And a (b) cyclopentadienyl bone
Transition Metal Compounds of Group IV of the Periodic Table Including Ligands with Cases
In the presence of an olefin polymerization catalyst containing
And an α-olefin having 3 to 20 carbon atoms.
And the (B-i) density is 0.850 to 0.980.
g / cm^Three(B-ii) 135 ° C, decalin
Intrinsic viscosity [η] measured in the range of 0.4 to 8 dl / g
Ethylene-α-olefin copolymer [B]
80% by weight of ethylene / α-olefin copolymer
Body composition (however, ethylene / α-olefin copolymer
What is [A] and ethylene / α-olefin copolymer [B]?
Are not the same) [II] Graft modified ethylene polymer or graft modified
And an ethylene copolymer, The above [I] ethylene / α-olefin copolymer composition
And the above [II] graft-modified ethylene polymer or
Weight ratio with the ethylene-modified ethylene copolymer ([I]: [I
I]) is in the range of 99.5: 0.5 to 60:40.
It is characterized by. [0010] Such an ethylene copolymer composition comprises:
The film is excellent in moldability and the obtained film has mechanical strength and transparency.
Excellent lightness and excellent adhesion to highly polar materials
I have. [0011] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the ethylene-based copolymer of the present invention will be described.
The polymer composition will be specifically described. Etch of the present invention
The lene-based copolymer composition includes [A] ethylene as described below.
-Α-olefin copolymer and [B] ethylene-α-O
[I] Ethylene-α-ole comprising a refin copolymer
Fin copolymer composition and [II] graft-modified ethylene
Formed from polymer or graft-modified ethylene copolymer
Have been. [Ethylene / α-olefin copolymer]
[A] Forming ethylene / α-olefin copolymer composition
The resulting ethylene / α-olefin copolymer [A]
Randomization of Tylene with α-olefin having 3 to 20 carbon atoms
It is a copolymer. Carbon used for copolymerization with ethylene
As the α-olefin of the formulas 3 to 20, propylene, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1-pente
1-octene, 1-decene, 1-dodecene, 1-tetradecene
1-hexadecene, 1-octadecene, 1-eicosene
And so on. [0013] 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 70-96% by weight
Derived from α-olefins having 3 to 20 carbon atoms
0 to 50% by weight, preferably 1 to 45% by weight
%, More preferably 2 to 35% by weight, most preferably
Desirably it is present in an amount of 4 to 30% by weight. 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 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of Such ethylene / α-olefin copolymers
The coalesced [A] has the characteristics shown in (A-i) and (A-ii) below.
(A-i) to (A-i)
v) It is more preferable to have the characteristics shown in
And has the following characteristics (Ai) to (A-viii).
Is particularly preferred. (A-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 / c.
m^Three, Most preferably from 0.900 to 0.930 g / cm^Threeof
It is desirable to be within the range. The density (d) is 2.90 at 190 ° C.
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. (A-ii) Measured at 135 ° C. in decalin
Intrinsic 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. (A-iii) Melt tension at 190 ° C.
(MT (g)) and melt flow rate (MFR)
But 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. The ethylene / α-O according to the present invention as described above.
Refin copolymer [A] has a large melt tension (MT).
And good moldability. The melt tension (MT
(G)) stretched the melted polymer at a constant speed
It is determined by measuring the stress at the time. That is,
The resulting polymer powder is melted in the usual way and then pelletized.
Use MT measuring machine manufactured by Toyo Seiki Seisakusho as a measurement sample
Resin temperature 190 ° C, extrusion speed 15mm / min, winding
Removal speed 10-20m / min, nozzle diameter 2.09mmφ,
The test was performed under the condition of a nozzle length of 8 mm. When pelletizing,
To ethylene / α-olefin copolymer [A]
Tri (2,4-di-t-butylphenyl) as a secondary antioxidant
F) 0.05% by weight of phosphate as heat stabilizer
N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butyl
0.1% by weight of tylphenyl) propionate, hydrochloric acid absorption
0.05% by weight of calcium stearate
I combined. The melt flow rate (MFR) is AST
According to MD1238-65T, 190 ° C, 2.16kg load
Measured below. (A-iv) Stress at 190 ° C. is 2.4 × 10⁶dyne /
cm^TwoFlow index defined by the shear rate when reaching
(FI (1 / second)) and melt flow rate (MF
R) FI <150 × MFR Preferably FI <140 × MFR More preferably, FI <130 × MFR It is desirable to satisfy the relationship shown by. The flow index (FI) is
While changing the speed, extrude the resin from the capillary and
Is determined by measuring the stress at the time. Sand
In addition, using a sample similar to the MT measurement, manufactured by Toyo Seiki Seisakusho,
Using a capillary flow property tester, resin temperature 190 ° C, shear
5 × 10 stress range^Four~ 3 × 10⁶dyne / cm^TwoAbout
Measured. The MFR of the resin to be measured (g / 10 minutes)
And the diameter of the nozzle is changed as follows. 0.5 mm when MFR> 20 1.0mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0mm when 0.8 ≧ MFR (Av) Molecular weight distribution measured by GPC (M
w / Mn, where Mw: weight average molecular weight, Mn: number average
(Molecular weight) is preferably in the range of 1.5 to 4. What
The molecular weight distribution (Mw / Mn) is GPC manufactured by Millipore.
It measured as follows using -150C. 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 and the mobile phase was o-dichloro
Benzene (Wako Pure Chemical Industries) and BH as an antioxidant
1.0 ml / min using 0.025% by weight of T (Takeda Pharmaceutical)
To adjust the sample concentration to 0.1% by weight.
Is 500 microliters and differential refraction as detector
A total was used. Standard polystyrene has a molecular weight Mw <10.
00 and Mw> 4 × 10⁶About Tosoh Corporation
No, 1000 <Mw <4 × 10⁶About Pressure
-Chemical Co., Ltd. was used. (A-vi) MT / (Mw / Mn) and FI / M
FR MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (However, the value of 0.03 × FI / MFR-3.0 is not 0
0 when full) 0.03 × FI / MFR + 1.0> MT / (Mw / Mn)
> 0.03 × FI / MFR-2.8 (However, the value of 0.03 × FI / MFR-2.8 is not 0
0 when it is full) 0.03 × FI / MFR + 0.8> MT / (Mw / Mn)
> 0.03 × FI / MFR-2.5 (However, the value of 0.03 × FI / MFR-2.5 is not 0
Satisfy 0)
Is desirable. It should be noted that as the value of Mw / Mn increases, the MT
Since the value becomes large, the value of Mw / Mn with respect to the value of MT
MT / (Mw / Mn) index to reduce the effect of
Was used. Similarly, the value of FI increases as the value of MFR increases.
The effect of the MFR value on the FI value
The index of FI / MFR was used to eliminate it. (A-vii) Differential scanning calorimeter (DSC)
Temperature at the maximum peak position of the endothermic curve (Tm
(° C)) and density (d) 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 with a differential scanning calorimeter (DSC).
Temperature at the maximum peak position of the determined endothermic curve (Tm (° C))
Is to pack about 5 mg of the sample into an aluminum pan at 10 ° C / min.
Heat to 0 ° C, hold at 200 ° C for 5 minutes, then 20 ° C
/ Minute to room temperature and then at 10 ° C / minute
From the endothermic curve. Measured by PerkinElmer
A DSC-7 type device manufactured by KK was used. (A-viii) n-decane soluble component at room temperature
The mass fraction (W (% by weight)) and the density (d) When MFR ≦ 10 g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9)^0.26× exp (−100 (d−
0.88)) + 0.1 Satisfies the relationship indicated by. The amount of the n-decane soluble component (the amount of the 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. As described above, 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 as described above
[A] can be said to have a narrow composition distribution. Ethylene α-having the above-mentioned properties
The olefin copolymer [A] is prepared by using (a) an organic alcohol
A minium oxy compound, (b) a transition metal compound, and
(C) carrier, if necessary (d) organoaluminum compound
In the presence of an olefin polymerization catalyst formed from
Preferably, (a) an organic aluminum oxy compound,
(B) a transition metal compound and (c) a carrier,
Optionally formed from (d) an organoaluminum compound
Ethylene and carbon in the presence of a catalyst for olefin polymerization
An α-olefin of Formulas 3 to 20 with the obtained copolymer
Density 0.850-0.980 g / cm^ThreeSo that
It can be produced by polymerizing. [Ethylene / α-olefin copolymer]
[B]] Forming an ethylene / α-olefin copolymer composition
The resulting ethylene / α-olefin copolymer [B]
Randomization of Tylene with α-olefin having 3 to 20 carbon atoms
It is a copolymer. Carbon used for copolymerization with ethylene
As the α-olefin of the formulas 3 to 20, propylene, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1-pente
1-octene, 1-decene, 1-dodecene, 1-tetradecene
1-hexadecene, 1-octadecene, 1-eicosene
And so on. 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 70-96% by weight
Derived from α-olefins having 3 to 20 carbon atoms
0 to 50% by weight, preferably 1 to 45% by weight
%, More preferably 2 to 35% by weight, most preferably
Desirably it is present in an amount of 4 to 30% by weight. The ethylene / α-olefin copolymer
The merging [B] is characterized by the following (B-i) and (B-ii).
It is preferable to have the following properties (B-i) to (B-i
v) It is particularly preferable to have the characteristics shown in
No. (Bi) 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 / c.
m^Three, Most preferably 0.920 to 0.950 g / cm^Threeof
It is desirable to be within the range. (B-ii) Measured in decalin at 135 ° C.
Intrinsic 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 / g
Is desirably within the range. (B-iii) Differential scanning calorimeter (DSC)
Temperature at the maximum peak position in the endothermic curve measured
(Tm (° C.)) and density (d) 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. (B-iv) Amount of n-decane soluble component at room temperature
The fraction (W (% by weight)) and the density (d) When MFR ≦ 10 g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 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 as described above
[B] can be said to have a narrow composition distribution. Further, ethylene / α-olefin copolymerization
In the form [B], the number of unsaturated bonds present in the molecule is the number of carbon atoms
Not more than 0.5 per 1,000 and one polymer molecule
It is desirable that the number be less than one. Ethylene α-having the above properties
The olefin copolymer [B] has (a)
Aluminum oxy compound, (b) transition metal compound,
And (c) a carrier, if necessary, (d) an organic aluminum.
Of olefin polymerization catalysts formed from rubber compounds
And ethylene and an α-olefin having 3 to 20 carbon atoms,
The density of the obtained copolymer is 0.850 to 0.980 g / c.
m^ThreeManufactured by copolymerization so that
Can be. Next, the ethylene / α-olefin copolymer of the present invention
Ethylene / α-olefin copolymer forming polymer composition
Catalyst used for copolymerization of coalesced [A] and [B]
Component (a) an organoaluminum oxy compound,
(B) including a ligand having a cyclopentadienyl skeleton
A transition metal compound of Group IV of the periodic table, (c) a carrier, and
(D) Specific description of the organoaluminum compound
You. 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. The aluminoxane as described above is, for example,
It can be manufactured by the method as described above. (1) Compounds containing adsorbed water or containing 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
A method of adding and reacting. (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) Decane, benzene, toluene, etc.
Organic aluminum such as trialkyl aluminum in a medium
Dimethyltin oxide, dibutyltin oxide
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 producing 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 organoaluminum compound as described above is
Used alone or in combination. Aluminoxane
Solvents used during production 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 material 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 organoaluminum 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
Used for copolymerization of copolymers [A] and [B]
(B) including a ligand having a cyclopentadienyl skeleton
Group IV transition metal compound (hereinafter referred to as “component (b)”)
May be described. ) Is specifically represented by the following formula [b-
I] is a transition metal compound. ML_x    ... [b-I] [Wherein M is a transition metal source selected from Group IVB of the periodic table.
L is a ligand that coordinates to the transition metal,
At least one L has a cyclopentadienyl skeleton.
Is a ligand having a cyclopentadienyl skeleton
L other than is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy
Group, aryloxy group, trialkylsilyl group, SO_ThreeR
Group (wherein R may have a substituent such as halogen)
A hydrocarbon group having 1 to 8 carbon atoms), a halogen atom or water
And x is the valence of the transition metal. ] In the general formula [b-I], 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, cyclopentadienyl group, methyl
Clopentadienyl group, dimethylcyclopentadienyl
Group, trimethylcyclopentadienyl group, tetramethyl
Cyclopentadienyl group, pentamethylcyclopentadi
Enyl group, ethylcyclopentadienyl group, methylethyl
Rucyclopentadienyl group, propylcyclopentadie
Group, methylpropylcyclopentadienyl group, butyral
Rucyclopentadienyl group, methylbutylcyclopenta
Such as dienyl group and hexylcyclopentadienyl group;
Alkyl substituted cyclopentadienyl group or indenyl
Group, 4,5,6,7-tetrahydroindenyl group, fluorenyl
And the like. These groups are
Even if it is substituted by a rusilsilyl group, halogen atom, etc.
Good. Among the ligands which coordinate to these transition metals,
Is particularly preferably an alkyl-substituted cyclopentadienyl group.
No. The compound represented by the general formula [b-I] is cyclope
When two or more ligands having an antadienyl skeleton are contained
Has two cyclopentadienyl skeletons
Ligands are alkylene such as ethylene and propylene
Group, substitution of isopropylidene, diphenylmethylene, etc.
Alkylene group, silylene group or dimethylsilylene group,
Diphenylsilylene group, methylphenylsilylene group, etc.
May be bonded via a substituted silylene group. Ligand having cyclopentadienyl skeleton
Specific examples of the ligand L other than
No. Examples of the hydrocarbon group having 1 to 12 carbon atoms include a
Alkyl group, cycloalkyl group, aryl group, aralkyl
And more specifically, as an alkyl group
Is methyl, ethyl, propyl, isopropyl
Group, butyl group, etc., and as the cycloalkyl group
Is, for example, a cyclopentyl group, a cyclohexyl group, etc.
Examples of the aryl group include a phenyl group and a tolyl group.
Illustrative examples of the aralkyl group include benzyl and neof.
And the like. 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 [bI ′]. R^Two _kR^Three _lR^Four _mR^Five _nM ... [bI '] (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. These cyclopentadi
Groups having an enyl skeleton may be
Alkylene group, isopropylidene, diphenylmethylene
Any substituted alkylene, silylene or dimethylsilicone
Len, diphenylsilylene, methylphenylsilylene group
May be bonded via a substituted silylene group or the like.
No. In this case, other ligands (for example, R^Fourand
R^Five) Is a group having a cyclopentadienyl skeleton,
Group, cycloalkyl group, aryl group, aralkyl group,
Alkoxy group, aryloxy group, trialkylsilyl
Group, SO_ThreeR, a halogen atom or a hydrogen atom. In the following, a transition metal wherein 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. In the above examples, 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. The zirconium compound as described above
And replace zirconium with titanium or hafnium
The obtained compound can also be used. In the present invention,
Used for the copolymerization of ren / α-olefin copolymer [A]
(B) Coordination having a cyclopentadienyl skeleton
The transition metal compound of Group IV of the periodic table containing
Transition metal compound represented by [b-II] or [b-III]
It is preferably an object. ML¹ _X      … [B-II] (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 number of 3 to 10
Having at least one group selected from hydrocarbon groups of
A substituted cyclopentadienyl group,
Ligands other than antadienyl groups L¹Has 1 to 12 carbon atoms
Hydrocarbon group, alkoxy group, aryloxy group, trial
A silyl group, a halogen atom or a hydrogen atom;
Is the valence of the transition metal M. ) ML^Two _X     ... [b-III] (Where M is a transition metal source selected from Group IVB of the periodic table)
Child and L^TwoIs a ligand that coordinates to the transition metal atom.
And at least two of these ligands L^TwoIs
Only 2 to 5 substituents selected from the group consisting of
A substituted cyclopentadienyl group having
Ligands other than pentadienyl groups L^TwoHas 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, tria
A rusilsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) Hereinafter, represented by the above general formula [b-II] or [b-III]
The transition metal compound will be described more specifically. In the above formula [b-II], M is the periodic table
A transition metal atom selected from Group IVB,
Is zirconium, titanium or hafnium, preferably
Preferable is zirconium. L¹Is a ligand coordinated to the transition metal atom M
And at least two of these ligands L¹Is
Cyclopentadienyl group, methylcyclopentadienyl
Group, an ethylcyclopentadienyl group, or
At least one selected from hydrocarbon groups having 3 to 10 carbon atoms
A substituted cyclopentadienyl group having various substituents
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,
Si group, aryloxy group, trialkylsilyl group, halogen
A hydrogen atom or a hydrogen atom. The substituted cyclopentadienyl group may be 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,
At least one substituent is a hydrocarbon group having 3 to 10 carbon atoms.
Other substituents may be methyl, ethyl or carbon.
It is a hydrocarbon group having a prime number of 3 to 10. Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include:
Include an alkyl group, a cycloalkyl group, an aryl group,
Examples include an aralkyl group. More specifically
Represents an n-propyl group, an isopropyl group, an n-butyl group,
Butyl, sec-butyl, t-butyl, pentyl,
Xyl, octyl, 2-ethylhexyl, decyl
Alkyl groups such as cyclopentyl group and cyclohexyl
Cycloalkyl groups such as phenyl groups, tolyl groups, etc.
Aryl such as benzyl and neophyl
A kill group 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,
As a (substituted) cyclopentadienyl group that coordinates to a metal transfer
Is preferably a substituted cyclopentadienyl group,
Cyclopentadienyl group substituted by three or more alkyl groups
Is more preferable, and a disubstituted cyclopentadienyl group is further preferable.
Preferred are 1,3-substituted cyclopentadienyl groups.
New In the general formula [b-II], the transition
(Substituted) cyclopentadienyl group coordinated to metal atom M
Ligand L other than¹Is a hydrocarbon group having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, trialkylsilyl group,
It is a halogen atom or a hydrogen atom. The hydrocarbon group having 1 to 12 carbon atoms includes
Alkyl group, cycloalkyl group, aryl group, aralkyl
Group, etc., and more specifically, methyl
Group, ethyl group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, t-butyl group, pen
Tyl, hexyl, octyl, 2-ethylhexyl
An alkyl group such as a benzyl group or a decyl group;
Cycloalkyl group such as clohexyl group; phenyl group,
Aryl groups such as tolyl group; benzyl group, neophyl group
And aralkyl groups. 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 above-mentioned general formula [b-II]
As the transition metal compound, bis (cyclopentadiene
Le) zirconium dichloride, bis (methylcyclopentene)
Tadienyl) zirconium dichloride, bis (ethyl
Clopentadienyl) zirconium dichloride, bis
(N-propylcyclopentadienyl) zirconium dik
Loride, bis (n-butylcyclopentadienyl) zirco
Dichloride, bis (n-hexylcyclopentadie
Nil) zirconium dichloride, bis (methyl-n-pro
Pyrcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-butylcyclopentadienyl) zirco
Dichloride, bis (dimethyl-n-butylcyclope
Antadienyl) zirconium dichloride, bis (n-butyl)
Rucyclopentadienyl) zirconium dibromide,
(N-butylcyclopentadienyl) zirconium meth
Xycyclolide, bis (n-butylcyclopentadienyl)
Zirconium ethoxycyclolide, bis (n-butylcyclo
Pentadienyl) 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, etc.
I can do it. In the above example, cyclopentadiene
Disubstituted nyl rings include 1,2- and 1,3-substituted,
Transformants include the 1,2,3- and 1,2,4-substituted. In the present invention,
In the zirconium compound as described above, zirconium
Replace metal with titanium or hafnium metal
Transition metal compounds can be used. These are represented by the general formula [b-II]
Among the transition metal compounds, bis (n-propylcyclope
Antadienyl) zirconium dichloride, bis (n-butyl)
Rucyclopentadienyl) zirconium dichloride, bi
(1-methyl-3-n-propylcyclopentadienyl) di
Ruconium dichloride, bis (1-methyl-3-n-butyl
Clopentadienyl) zirconium dichloride, especially
preferable. In the general formula [b-III], 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 coordinated to the transition metal atom M
And at least two of these ligands L^TwoIs
Only 2 to 5 substituents selected from a tyl group and an ethyl group
Substituted cyclopentadienyl groups, each of which is the same
Or different. This substituted cyclopenta
A dienyl group is a substituted cyclopentene having two or more substituents.
A substituted cycle having 2 to 3 substituents, which is a tadienyl group;
And preferably a dipentadienyl group.
More preferably, it is a lopentadienyl group,
Particularly preferred is a substituted cyclopentadienyl group. In the above formula [b-III], the transition metal
Other than a substituted cyclopentadienyl group coordinating to the atom M
Ligand L^TwoIs L in the above general formula [b-II]¹As well as carbon
Hydrocarbon groups of 1 to 12 groups, alkoxy groups, aryloxy
Group, trialkylsilyl group, halogen atom or hydrogen atom
I am a child. The compound represented by the general formula [b-III]
As the transition metal compound, bis (dimethylcyclopentane
Dienyl) zirconium dichloride, bis (diethyl
Clopentadienyl) zirconium dichloride, bis
(Methylethylcyclopentadienyl) zirconiumdi
Chloridebis (dimethylethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopenta
Dienyl) zirconium dibromide, bis (dimethyl
Clopentadienyl) zirconium methoxy chloride,
Bis (dimethylcyclopentadienyl) zirconium
Tokicyclolide, bis (dimethylcyclopentadienyl)
B) zirconium butoxycyclolide, bis (dimethylsi
Clopentadienyl) zirconium diethoxide, bis
(Dimethylcyclopentadienyl) zirconium methyl
Chloride, bis (dimethylcyclopentadienyl) silyl
Conium dimethyl, bis (dimethylcyclopentadienyl
B) zirconium benzyl chloride, bis (dimethyl
Clopentadienyl) zirconium dibenzyl, bis
(Dimethylcyclopentadienyl) zirconium phenyl
Luchloride, bis (dimethylcyclopentadienyl) di
And ruconium hydride chloride.
Note that, in the above example, the cyclopentadienyl ring
Substitutes include 1,2- and 1,3-substitutes, tri-substitutes include 1,2,
Includes 3- and 1,2,4-substitutes. In the present invention, as described above,
A zirconium compound, a zirconium metal,
Transition metal replaced with titanium metal or hafnium metal
Compounds can be used. These are represented by the general formula [b-III]
Among the transition metal compounds, bis (1,3-dimethylcyclo
Pentadienyl) zirconium dichloride, bis (1,3-
(Diethylcyclopentadienyl) zirconium dichloride
De, bis (1-methyl-3-ethylcyclopentadienyl)
Zirconium dichloride is particularly preferred. In the present invention, ethylene / α-olefin
In producing the polymer [A], (b) a transition metal compound
A transition metal compound represented by the above general formula [b-II]
And at least one selected from the above general formula [b-III]
At least one selected from transition metal compounds represented by
Are preferably used in combination. In particular,
Bis (1,3-n-butylmethylcyclopentadienyl) silyl
Conium dichloride and bis (1.3-dimethylcyclopenta
Dienyl) combination with zirconium dichloride,
(1,3-n-propylmethylcyclopentadienyl) zyl
Conium dichloride and bis (1,3-dimethylcyclopenta
Dienyl) combination with zirconium dichloride,
(N-butylcyclopentadienyl) zirconium dic
Loride and bis (1,3-dimethylcyclopentadienyl) di
Combinations with ruconium dichloride are preferred. The transition metal represented by the above general formula [b-II]
At least one transition gold selected from compound (b-II)
And a transition metal represented by the general formula [b-III]
At least one transition gold selected from compound (b-III)
The genus compound is 99/1 to 1 in molar ratio (b-II / b-III).
50/50, preferably 97/3 to 70/30, more preferably
Preferably 95/5 to 75/25, most preferably 90 /
The amount used should be in the range of 10-80 / 20.
Is desirable. Hereinafter, the term “component (b)” will be referred to as
Selected from the transition metal compound (b-II) represented by the formula [b-II]
And at least one kind represented by the above general formula [b-III]
At least one selected from transition metal compounds (b-III)
Transition metal compound catalyst component containing at least one
is there. In the present invention, ethylene / α-olefin
Used for copolymerization of copolymers [A] and [B]
(C) a carrier (hereinafter sometimes referred to as “component (c)”);
You. ) Is an inorganic or organic compound having a particle size
Granules of 10 to 300 μm, preferably 20 to 200 μm
Solids in the form of particles or fine particles are used. Of these, inorganic
As the compound, a porous oxide is preferable.
iO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, Ca
O, ZnO, BaO, ThO_TwoOr a mixture of these,
For example, SiO_Two-MgO, SiO_Two-Al_TwoO_Three, SiO_Two-Ti
O_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-
MgO can be exemplified. Among them, SiO
_TwoAnd Al_TwoO_ThreeAt least one selected from the group consisting of
It is preferable to use one containing the above component as a main component. The above inorganic oxide contains a small amount of Na._TwoCO
_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 (N
O_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonates such as O, sulfates,
It does not matter if it contains nitrate or oxide components. Such a carrier (c) depends on the kind and the production method.
Although their properties are different, they are preferably used in the present invention.
The carrier has a specific surface area of 50 to 1000 m^Two/ G, preferably
Is 100-700m^Two/ G and a pore volume of 0.3 to
2.5cm^Three/ G is desirable. The carrier is required
100-1000 ° C., preferably 150-70 ° C.
It is used after firing at 0 ° C. In such a carrier (c), the amount of adsorbed water is
Less than 1.0% by weight, preferably less than 0.5% by weight.
Is desirable, and the surface hydroxyl group is preferably 1.0% by weight or more.
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 (c) (% by weight)
And the amount of surface hydroxyl groups (% by weight) are determined as follows.
Can be [Amount of adsorbed water] at a temperature of 200 ° C. under normal pressure and nitrogen flow
The weight loss after drying for an hour is defined as 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. Surface hydroxyl group content (% by weight) = ｛(XY) /
X｝ 100 Further, as a carrier (c) that can be used in the present invention,
Is an organic compound having a particle size in the range of 10 to 300 μm.
Granular or particulate solids can be mentioned. This
These organic compounds include ethylene, propylene, and 1-butyl.
Α- having 2 to 14 carbon atoms such as ten- or 4-methyl-1-pentene
There is a (co) polymer produced mainly from olefins
Is mainly composed of vinylcyclohexane and styrene.
The polymer or copolymer to be formed can be exemplified.
You. In the present invention, ethylene / α-olefin
Catalyst used for copolymerization of copolymers [A] and [B]
Is the above (a) organoaluminum oxy compound, (b)
Formed from a transition metal compound and (c) a carrier,
Optionally containing (d) an organoaluminum compound
You may. (D) Organic aluminum optionally used
Compound (hereinafter sometimes referred to as “component (d)”).
You. ) Are, for example, those represented by the following general formula [IV].
Aluminum compounds can be exemplified. R¹ _nAlX_3-n  … [IV] (Where R¹Is a hydrocarbon group having 1 to 12 carbon atoms, and X
Is a halogen atom or a hydrogen atom, and n is 1 to 3.
You. ) In the above general formula [IV], R¹Is charcoal having 1 to 12 carbon atoms
Hydrogen groups such as alkyl, cycloalkyl or
Although it is a reel group, specifically, a methyl group, an ethyl group,
n-propyl group, isopropyl group, isobutyl group, pliers
Group, hexyl group, octyl group, cyclopentyl group,
Examples include a clohexyl group, a phenyl group and a tolyl group. Such an (d) organoaluminum compound
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 Also, (d) an organoaluminum compound
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, -SiR⁶ _Three
Group or -N (R⁷) AlR⁸ _TwoAnd n is 1-2.
R^Two, R^Three, R^FourAnd R⁸Represents a methyl group, an ethyl group,
Isopropyl, isobutyl, cyclohexyl,
And a R group such as^FiveIs hydrogen atom, methyl group, ethyl
Group, isopropyl group, phenyl group, trimethylsilyl group
And R⁶And R⁷Is a methyl group, an ethyl group, etc.
It is. ) Specific examples of such an organoaluminum compound include:
The following compounds are used. (1) R¹ _nAl (OR^Two)_3-nA compound represented by, for example, di
Methyl aluminum methoxide, diethyl aluminum
Ethoxide, diisobutylaluminum methoxide
Th (2) R¹ _nAl (OSiR^Three _Three)_3-nCompound represented by, for example
If Et_TwoAl (OSi Me_Three), (Iso-Bu)_TwoAl (OSiMe_Three),
(iso-Bu)_TwoAl (OSiEt_Three) Such; (3) R¹ _nAl (OALR^Four _Two)_3-nCompound represented by
For example, Et_TwoAlOAlEt_Two, (Iso-Bu)_TwoAlOAl (iso-Bu)
_TwoSuch; (4) R¹ _nAl (NR^Five _Two)_3-nA compound represented by, for example,
Me_TwoAlNEt_Two, Et_TwoAlNHMe, Me_TwoAlNHEt,
Et_TwoAlN (SiMe_Three)_Two, (Iso-Bu)_TwoAlN (SiMe_Three)_Two What
Which; (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-nCompound represented by
Object, eg Et_TwoAlN (Me) AlEt_Two, (Iso-Bu)_TwoAlN
(Et) Al (iso-Bu)_TwoSuch . Represented by the above general formulas [IV] and [V]
Among the organoaluminum compounds, the general formula R¹ _ThreeAl, R¹
_nAl (OR^Two)_3-n, R¹ _nAl (OAlR^Four _Two)_3-nRepresented by
Compounds are preferred, in particular R is an isoalkyl group, n
= 2 is preferred. In the present invention, ethylene / α-olefin
In producing the polymers [A] and [B],
Component (a), component (b) and component (c), as required
Prepared by contacting component (d) according to
A catalyst is used. In this case, the components (a) to (d)
The order of contact may be arbitrarily selected, but preferably the component (c)
And component (a) are mixed and contacted, and then component (b) is mixed.
Contact, and if necessary, mixed contact with component (d)
Let it. Wherein component (b) is a mixture of two or more transition metal compounds;
Two types of the component (b)
After mixing the above transition metal compounds in advance, mix with other components
It is preferable to make contact. The contact of the above components (a) to (d) is not
Can be carried out in an active hydrocarbon solvent and used for catalyst preparation
Specific examples of the inert hydrocarbon solvent used include propane.
, Butane, pentane, hexane, heptane, octa
Aliphatic hydrocarbons such as carbohydrate, decane, dodecane and kerosene;
Clopentane, cyclohexane, methylcyclopentane
Alicyclic hydrocarbons such as benzene, toluene, xylene
Aromatic hydrocarbons such as ethylene chloride, chloroben
Halogenated hydrocarbons such as zen, dichloromethane, etc.
May be a mixture thereof. Component (a), component (b) and component
(C) when mixing and contacting the component (d) if necessary
Component (b) is usually 5 × 10 5 per gram of component (c).^-6
~ 5 × 10 ^-FourMole, preferably 10^-Five~ 2 × 10^-FourMole
And the concentration of component (b) is about 10^-Four~ 2x
10^-2Mol / liter (solvent), preferably 2 × 10^-Four
-10^-2It is in the range of mol / liter (solvent). component
Source of aluminum of (a) and transition metal in component (b)
The atomic ratio (Al / transition metal) is usually 10 to 500, preferably
20 to 200. Ingredients used as needed
(D) aluminum atom (Al-d) and component (a)
Atomic ratio of luminium atom (Al-a) (Al-d / Al-a)
Is usually in the range of 0.02 to 3, preferably 0.05 to 1.5.
It is an enclosure. Component (a), component (b) and component (c),
Mixing temperature for mixing and contacting component (d) if necessary
Is usually -50 to 150C, preferably -20 to 120.
C. and a contact time of 1 minute to 50 hours, preferably 10 minutes.
Minutes to 25 hours. The polymerization catalyst obtained as described above (solid
(Catalyst component) is derived from component (b) per gram of component (c)
5 × 10 transition metal atoms^-6~ 5 × 10^-FourGram Hara
Child, preferably 10^-Five~ 2 × 10^-FourCarried by the amount of gram atom
Component (a) and component per gram of component (c)
10 aluminum atoms derived from (d)^-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. Ethylene / α-olefin copolymer [A]
And the catalyst used in the production of [B] are as described above.
Component (a), component (b) and component (c), as required
By pre-polymerizing the olefin in the presence of component (d)
Prepolymerization catalyst may be used. The prepolymerization is as described above.
Of component (a), component (b) and component (c)
In the presence, if necessary, in the presence of component (d), inert hydrocarbon
This can be done by introducing an olefin into an organic solvent.
it can. The above components (a) to (c) are converted to the solid
Preferably, a catalyst component is formed. in this case,
In addition to the solid catalyst component, component (a) and / or
May add the component (d). The olefin used in the prepolymerization is
Ethylene and α-olefin having 3 to 20 carbon atoms
Propylene, 1-butene, 1-pentene, 4-methyl
1-pentene, 1-hexene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, etc.
You. Among these, ethylene or polymerization with ethylene
In particular, a combination with an α-olefin used in
New In the prepolymerization, the component (b) is
In terms of a transition metal atom derived from the component (b),
10^-6~ 2 × 10^-2Mol / l (solvent), preferably
Is 5 × 10^-Five-10^-2For use in moles / liter (solvent)
The component (b) is usually 5 × 1 per 1 g of the component (c).
0^-6~ 5 × 10^-FourMole, preferably 10^-Five~ 2 × 10 ^-Four
Used in molar amounts. Aluminum of component (a) and components
The atomic ratio (Al / transition metal) to the transition metal in (b) is
Usually it is 10-500, preferably 20-200. Must
Aluminum atom of component (d) optionally used
(Al-d) and the aluminum atom (Al-a) of the component (a)
The atomic ratio (Al-d / Al-a) is usually from 0.02 to 3, preferably
In the range of 0.05 to 1.5. Pre-polymerization temperature is -2
0 to 80 ° C., preferably 0 to 60 ° C .;
The combined time is 0.5 to 100 hours, preferably 1 to 50 hours
It is about. The prepolymerized catalyst is, for example,
Prepared. That is, the carrier (component (c)) is
Suspend with hydrogen chloride. Then the organic alcohol was added to this suspension.
Add the minium oxy compound (component (a))
To react for a while. Thereafter, the supernatant was removed and the resulting solid component was removed.
The fraction is resuspended with an inert hydrocarbon. Transition gold into this system
A genus compound (component (b)) was added and reacted for a predetermined time.
Thereafter, the supernatant is removed to obtain a solid catalyst component. Then organic
Inert carbon containing luminium compound (component (d))
The solid catalyst component obtained above is added to hydrogen, and
By introducing refine, a prepolymerized catalyst is obtained. Olefin (co) polymerization formed by prepolymerization
The body is 0.1-500 g / g of carrier (c), preferably
Is from 0.2 to 300 g, more preferably from 0.5 to 200 g
Desirably, it is an amount. In addition, the pre-polymerization catalyst
Component (b) per gram of body (c) contains about 5 as a transition metal atom.
× 10^-6~ 5 × 10^-FourGram atoms, preferably 10^-Five~
2 × 10^-FourComponent (a) and gram atoms.
And the aluminum atom (Al) derived from the component (d)
Mol per transition metal atom (M) derived from component (b)
5-200, preferably 10-15, in ratio (Al / M)
It is desirable that the carrier is carried in an amount in the range of 0. The prepolymerization can be carried out in a batch system or a continuous system.
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
Preparing the prepolymer to be 0.5-5 dl / g
It is desirable. Forming the Ethylene Copolymer Composition of the Present Invention
Ethylene-α-olefin copolymer [A] and
[B] is ethylene in the presence of the catalyst as described above,
Α-olefin having 3 to 20 carbon atoms, for example, propylene, 1
-Butene, 1-pentene, 1-hexene, 4-methyl-1-pente
1-octene, 1-decene, 1-dodecene, 1-tetradecene
1-hexadecene, 1-octadecene, 1-eicosene
Is obtained by copolymerizing In the present invention, ethylene and α-olefin
Is carried out in the gas phase or in the liquid phase of a slurry.
You. In slurry polymerization, an inert hydrocarbon is used as a solvent.
Or the olefin itself can be used as the solvent.
You. Inert carbon used in slurry polymerization
Specific examples of the hydrogen hydride solvent 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.
In such a case, the above-mentioned catalyst is used as a transition metal in the polymerization reaction system.
The concentration of a genus atom is usually 10^-8-10^-3Gram atom /
Liters, preferably 10^-7-10^-FourGram atom / Li
Preferably, it is used in an amount of torr. In the polymerization, the carrier is supported on a carrier.
Organic aluminum oxy compound (component (a)) and
In addition to the aluminum compound (component (d)),
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. In the present invention, a slurry polymerization method is carried out.
The polymerization temperature is usually -50 to 100 ° C, preferably
In the range of 0 to 90 ° C.
The polymerization temperature is usually 0 to 120 ° C., preferably 20 ° C.
-100 ° C. 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. Further, the polymerization is carried out in two or more stages under different reaction conditions.
It is also possible to perform it separately. [[I] Ethylene / α-olefin copolymer composition]
Ethylene forming the ethylene copolymer composition of the invention
α-olefin copolymer composition [I]
・ Α-olefin copolymer [A] and ethylene α-ole
Consisting of a fin copolymer [B], ethylene-α-ole
The fin copolymer [A] is 20 to 90% by weight, preferably
Ethylene-α-olef contained in an amount of 40-75% by weight
The copolymer [B] is 10 to 80% by weight, preferably 2% by weight.
Desirably, it is contained in an amount of 5 to 60% by weight. (However
And ethylene / α-olefin copolymer [A]
(This is not the same as α-olefin copolymer [B].) Ethylene / α-olefin copolymer [A]
And [B] are ethylene / α-olefin copolymers
Density of [A] and ethylene / α-olefin copolymer
The ratio ([A] / [B]) to the density of [B] is preferably 1
Less, more preferably 0.930 to 0.999
Used in combination. Such ethylene / α-olefin copolymers
The coalesced composition [I] is as shown in the following (i) to (vi)
Preferably, it has properties. (I) Density 0.850-0.980 g / cm^Three, Preferred
0.890-0.955 g / cm^Three, More preferably
0.900-0.950 g / cm^ThreeHoped to be in the range of
Good. (Ii) At 190 ° C. under a load of 2.16 kg
The composition has a melt flow rate (MFR) of 0.1 to 0.1
100 g / 10 min, preferably 0.2 to 50 g / 10 min
Is desirably within the range. (Iii) Melt tension at 190 ° C.
(MT (g)) and melt flow rate (MFR)
But, MT ≧ 2.2 × MFR^-0.84 It is desirable to satisfy the relationship shown by. (Iv) 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
(MFR) 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 (Tm) at the maximum peak position of the measured endothermic curve
(° C.)) and density (d) 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. (Vii) Amount of n-decane soluble component at room temperature
The fraction (W (% by weight)) and the density (d) When MFR ≦ 10 g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10g / 10min W <80 × (MFR-9)^0.26× exp (−100 (d−
0.88)) + 0.1 It is desirable to satisfy the relationship shown by. Forming the Ethylene Copolymer Composition of the Present Invention
Ethylene-α-olefin copolymer composition is known
Can be produced using the method of, for example, the following
It can be manufactured by such a method. (1) Ethylene / α-olefin copolymer
[A], an ethylene / α-olefin copolymer [B],
Extruder, kneader
A method of mechanically blending using a method such as (2) Ethylene / α-olefin copolymer
[A], an ethylene / α-olefin copolymer [B],
And any other components that may be added as desired
For example; hexane, heptane, decane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene and xylene)
And then removing the solvent. (3) Ethylene / α-olefin copolymer
[A], 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
To copolymerize a len / α-olefin copolymer [B]
Can also be produced. [[II] Graft-modified ethylene (co) polymerization
[I body] to form the ethylene copolymer composition of the present invention [I
I] Graft-modified ethylene (co) polymer
Merged or ethylene and α-olefin having 3 to 20 carbon atoms
Modified by graft modification of a copolymer with a polar monomer
It is an ethylene (co) polymer. Forming the Ethylene Copolymer Composition of the Present Invention
Ethylene copolymers, ethylene and α-olefin
And the molar ratio (ethylene / α-olefin) is α-olefin
Although it depends on the type of pin, generally it is 1/99 to 99
/ 1, preferably 50/50 to 95/5. Above
When the α-olefin is propylene,
It is preferably 50/50 to 90/10,
When the refin is an α-olefin having 4 or more carbon atoms
Is preferably 80/20 to 95/5. Such an ethylene polymer or ethylene
As the copolymer, the polarities measured in decalin at 135 ° C were used.
The limiting viscosity [η] is 0.4 to 7 dl / g, preferably 0.5 to 7 dl / g.
It is desirable to be in the range of 5 dl / g. Α-Olefi constituting ethylene copolymer
Α-olefins having 3 to 20 carbon atoms, such as
Propylene, butene-1, pentene-1, 2-methylbutene
-1,3-methylbutene-1, hexene-1,3-methylpentene
-1,4-methylpentene-1,3,3-dimethylbutene-1, hept
Ten-1, methylhexene-1, dimethylpentene-1, tri
Methylbutene-1, ethylpentene-1, octene-1, methyl
Lupentene-1, dimethylhexene-1, trimethylpente
1, ethylhexene-1, methylethylpentene-1, di
Ethylbutene-1, propylpentene-1, decene-1, methyl
Lunonene-1, dimethyl octene, trimethyl heptene-
1, ethyl octene-1, methyl ethyl heptene-1, die
Tylhexene-1, dodecene-1, hexadodecene and
Mention may be made of these mixtures. Among them, carbon number 3
Especially preferred are α-olefins of from 10 to 10. In the present invention, ethylene (co) polymerization
The body is ethylene or α having 3 to 20 carbon atoms as described above.
-Besides repeating units derived from olefins,
From other compounds polymerizable with ren or α-olefins
It may have a derived repeating unit. Examples of such other compounds include, for example, a chain
Polyene compound and cyclic polyene compound, cyclic mono
And ene compounds. These polyene compounds are
2 or more conjugated or non-conjugated olefinic double bonds
A polyene having such a linear polyene compound
Examples of 1,4-hexadiene, 1,5-hexadiene,
1,7-octadiene, 1,9-decadiene, 2,4,6-octatri
Ene, 1,3,7-octatriene, 1,5,9-decatriene and
And divinylbenzene. Examples of the cyclic polyene compound include:
1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-
Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadi
Ene, dicyclopentadiene, dicyclohexadiene,
5-ethylidene-2-norbornene, 5-vinyl-2-norbornene
, 5-isopropylidene-2-norbornene, methyl hydride
Loindene, 2,3-diisopropylidene-5-norbornene
2-ethylidene-3-isopropylidene-5-norbornene
2-ethylidene-3-isopropylidene-5-norbornene
And 2-propenyl-2,5-norbornadiene and the like
Can be Further, examples of the cyclic monoene include cycloalkyl
Propene, cyclobutene, cyclopentene, cyclohexene
Sen, 3-methylcyclohexene, cycloheptene, cyclone
Looctene, cyclodecene, cyclododecene, tetracy
Clodecene, octacyclodecene and cycloeicosese
Monocycloalkenes such as norbornene, 5-methyl
2-norbornene, 5-ethyl-2-norbornene, 5-isobu
Tyl-2-norbornene, 5,6-dimethyl-2-norbornene,
5,5,6-trimethyl-2-norbornene and 2-bornene
Which bicycloalkene; 2,3,3a, 7a-tetrahydro-4,7-
Methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7
Tricycloalkenes such as -methano-1H-indene; 1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphtha
Len, as well as these compounds, 2-methyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphtha
Len, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-propyl-1,4,5,8-dimeta
No-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-f
Xyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahi
Dronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl
-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro
Naphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-
1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydrona
Phthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-di
Methano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and
And 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8
Tetracycloalkene such as a-octahydronaphthalene
Hexacyclo [6,6,1,1^3.6, 1^10.13, 0^2.7, 0^9.14]
Ptadecene-4, pentacyclo [8,8,1^2.9, 1^4.7, 1^11.18,
0,0^3.8, 0^12.17Hen-eicosene-5, octacyclo [8,
8,1^2.9, 1^4.7, 1^11.18, 0,0^3.8, 0^12.17] Such as docosen-5
List cyclic monoene compounds such as polycycloalkene
be able to. Further, ethylene (co) polymer is
Containing structural units derived from substituted styrene
Is also good. Such diene components may be used alone or in combination.
They can be used together. Also, such a diene
The content of the component is usually 1 to 20 mol%, preferably 2 mol%.
１５15 mol%. The diene component may be used alone or
They can be used in combination. Also, such a di
The content of the ene component is usually 1 to 20 mol%, preferably
Is 2 to 15 mol%. [II] Graft-modified ethylene (co) polymer
Is ethylene as described above in the presence of a radical initiator.
Reacting a (co) polymer with a polar monomer described below
Can be obtained. Examples of polar monomers include hydroxyl group-containing ethylene.
Unsaturated compounds, amino group-containing ethylenically unsaturated compounds
Substances, epoxy group-containing ethylenically unsaturated compounds, aromatic
Compounds, unsaturated carboxylic acids or their derivatives,
Nyl ester compounds, vinyl chloride and the like. Specifically, hydroxyl-containing ethylenically unsaturated
As the compound, hydroxyethyl (meth) acrylate
G, 2-hydroxypropyl (meth) acrylate, 3-h
Droxypropyl (meth) acrylate, 2-hydroxy
-3-phenoxy-propyl (meth) acrylate, 3-
Rollo-2-hydroxypropyl (meth) acrylate,
Lyserine mono (meth) acrylate, pentaerythritol
Mono (meth) acrylate, trimethylolpropa
Mono (meth) acrylate, tetramethylolethane
Mono (meth) acrylate, butanediol mono (me
TA) acrylate, polyethylene glycol mono (me
TA) acrylate, 2- (6-hydroxyhexanoyloxy)
(S) (meth) acrylic acid S such as ethyl acrylate
Ter; 10-undecene-1-ol, 1-octen-3-o
, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl bi
Nyl ether, N-methylolacrylamide, 2- (meth
A) Acroyloxyethyl acid phosphate,
Glycerin monoallyl ether, allyl alcohol,
Riloxyethanol, 2-butene-1,4-diol, glycer
Phosphorus monoalcohol and the like. The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group,
Such a compound includes an amino group represented by the following formula:
Or vinyl compounds having at least one kind of substituted amino group
Monomers can be mentioned. [0144] Embedded image In the formula, R¹Is a hydrogen atom, a methyl group or an
A tyl group;^TwoIs a hydrogen atom, having 1 to 12 carbon atoms,
Preferably an alkyl group having 1 to 8 carbon atoms, 6 to 12 carbon atoms,
Preferably it is 6 to 8 cycloalkyl groups. The above
The alkyl and cycloalkyl groups of the above have further substituents.
May be. Such amino group-containing ethylenically unsaturated compounds
As the compound, specifically, (meth) acrylic acid amide
Noethyl, propylaminoethyl (meth) acrylate,
Dimethylaminoethyl methacrylate, (meth) acrylic
Aminopropyl acrylate, phenylaminoethyl methacrylate
And cyclohexylaminoethyl methacrylate
Alkyl ester of acrylic acid or methacrylic acid
Conductors; N-vinyldiethylamine and N-acetylvinyl
Vinylamine derivatives such as ruamine; allylamido
Methacrylamine, N-methylacrylamine, N, N-
Dimethylacrylamide and N, N-dimethylaminop
Allylamine derivatives such as propylacrylamide;
Acts such as acrylamide and N-methylacrylamide
Rilamide derivatives; aminos such as p-aminostyrene
Tylenes; 6-aminohexylsuccinimide, 2-amino
Ethyl succinimide and the like are used. Epoxy group-containing ethylenically unsaturated compound
Is a polymerizable unsaturated bond and epoxy group in one molecule.
Is a monomer having at least one or more such
The most common epoxy group-containing ethylenically unsaturated compounds are
Physically, glycidyl acrylate, glycidyl methax
Mono and diglycidyl esters of maleic acid, such as
Stele, mono and diglycidyl esters of fumaric acid,
Mono and diglycidyl esters of crotonic acid, tetra
Mono- and diglycidyl esters of hydrophthalic acid;
Mono- and glycidyl esters of taconic acid, butenetri
Mono- and diglycidyl esters of carboxylic acids, citrus
Mono- and diglycidyl esters of conic acid, endo-cy
Subbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid
(Nadic acid^TM) Mono- and diglycidyl esters,
Endo-cis-bicyclo [2.2.1] hept-5-en-2-methy
2,3-dicarboxylic acid (methylnadic acid^TM) Things
And diglycidyl esters and mono- and allylsuccinic acid
Dicarboxylic acids such as
Lucyl glycidyl ester (monoglycidyl ester
In the case where the alkyl group has 1 to 12 carbon atoms, p-styrene carb
Alkyl glycidyl ester of boric acid, allyl glycidyl
Ether, 2-methylallyl glycidyl ether, styrene
Len-p-glycidyl ether, 3,4-epoxy-1-butene,
3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pe
Content, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy
Xyl-1-hexene, vinylcyclohexene monoxide
And the like. The aromatic vinyl compound is represented by the following formula:
Compounds to be used. [0149] Embedded image In the above formula, R¹And R^TwoEach
Independently a hydrogen atom or an alkyl having 1 to 3 carbon atoms
A methyl group, an ethyl group, a propyl group
And isopropyl groups. Ma
R^ThreeIs a hydrocarbon group having 1 to 3 carbon atoms or halogen
Represents a methyl atom, an ethyl group,
Ropyl and isopropyl groups and chlorine and bromine atoms
And iodine atoms. Also,
n usually represents an integer of 0 to 5, preferably 1 to 5. Specific examples of such aromatic vinyl compounds
Examples include styrene, α-methylstyrene, o-methyl
Styrene, p-methylstyrene, m-methylstyrene, p-k
Lorostyrene, m-chlorostyrene and p-chloromethyl
Styrene, 4-vinylpyridine, 2-vinylpyridine, 5-d
Tyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,
2-isopropenylpyridine, 2-vinylquinoline, 3-vinyl
Luisoquinoline, N-vinyl carbazole, N-vinyl pyro
Ridon and the like can be mentioned. As unsaturated carboxylic acids, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrofur
Talic acid, itaconic acid, citraconic acid, crotonic acid, iso
Crotonic acid, norbornene dicarboxylic acid, bicyclo [2,
2,1] Unsaturated carbon such as hept-2-ene-5,6-dicarboxylic acid
Rubonic acid, or their anhydrides or their derivatives
Conductors (eg acid halides, amides, imides, esters
Etc.). Examples of specific compounds include chloride
Malenyl, malenimide, maleic anhydride, italic anhydride
Conic acid, citraconic anhydride, tetrahydrophthalic anhydride
Acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid
Acid anhydride, dimethyl maleate, monomethyl maleate
, Diethyl maleate, diethyl fumarate, itacone
Acid dimethyl, diethyl citraconic acid, tetrahydrophthalate
Dimethyl luate, bicyclo [2,2,1] hept-2-ene-5,6-
Dimethyl dicarboxylate, hydroxyethyl (meth) ac
Relevant, hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, amino methacrylate
Examples include ethyl and aminopropyl methacrylate
be able to. Among these, (meth) acrylic acid,
Maleic anhydride, hydroxyethyl (meth) acrylate
G, glycidyl methacrylate, aminop-methacrylate
Ropyr is preferred. As an example of the vinyl ester compound, acetic acid
Vinyl, vinyl propionate, n-vinyl butyrate, isobutyric acid
Vinyl, vinyl pivalate, vinyl caproate, versa
Tick vinyl, vinyl laurate, bi-stearate
Nil, vinyl benzoate, p-t-butyl vinyl benzoate, sa
Vinyl lithate, vinyl cyclohexanecarboxylate, etc.
Can be mentioned. The above-mentioned polar monomer is the above-mentioned ethylene / α-
Usually, 1 part by weight based on 100 parts by weight of the olefin copolymer is used.
Used in an amount of -100 parts by weight, preferably 5-80 parts by weight
Is done. As the radical initiator, an organic peroxide may be used.
Or an azo compound. Organic peracid
Specific examples of the compound include dicumyl peroxide,
Di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexane, 2,5-dimethyl-2,5-bis
(t-butylperoxy) hexyne-3,1,3-bis (t-butyl
Peroxyisopropyl) benzene, 1,1-bis (t-butyl
Peroxy) balarate, benzoyl peroxide, t
-Butyl peroxybenzoate, acetyl peroxa
Id, isobutyryl peroxide, octanoyl par
Oxide, decanoyl peroxide, lauroylpa
-Oxide, 3,5,5-trimethylhexanoyl peroxy
Side and 2,4-dichlorobenzoyl peroxide,
m-toluyl peroxide and the like.
In addition, azo compounds include azoisobutyronitrile,
Methyl azoisobutyronitrile and the like can be mentioned.
You. Such a radical initiator can be obtained by the above-mentioned ethylene polymerization.
Per 100 parts by weight of olefin / α-olefin copolymer
Generally used in an amount of 0.001 to 10 parts by weight
Is desirable. The radical initiator is ethylene • α as it is.
-Use mixed with olefin copolymer and polar monomer
The radical initiator can be used in small quantities.
It can also be used by dissolving it in an organic solvent. Used here
Organic solvents that can dissolve the radical initiator
It can be used without particular limitation as long as it is an organic solvent.
Wear. Such organic solvents include benzene and toluene.
Aromatic hydrocarbon solvents such as butane and xylene; pentane
, Hexane, heptane, octane, nonane and deca
Aliphatic hydrocarbon solvents such as cyclohexane;
Such as rucyclohexane and decahydronaphthalene
Alicyclic hydrocarbon solvents: chlorobenzene, dichlorobe
Benzene, trichlorobenzene, methylene chloride, chloropho
Salts such as lume, carbon tetrachloride and tetrachloroethylene
Hydrogenated hydrocarbons: methanol, ethanol, n-propynol
, Iso-propanol, n-butanol, sec-butanol
Alcohol solvents such as tert-butanol and tert-butanol;
Ton, methyl ethyl ketone and methyl isobutyl keto
Solvents such as ketones; ethyl acetate and dimethyl phthalate
Ester solvents such as dimethyl ether;
Tyl ether, di-n-amyl ether, tetrahydroph
Ether solvents such as orchids and dioxyanisole
Can be mentioned. In addition, ethylene / α-olefin copolymer
When graft-modifying the compound, a reducing substance may be used.
No. The reducing substance is obtained by graft-modified ethylene α
To improve the amount of grafting in -olefin copolymers
Has an action. The reducing substances include iron (II) ions,
Rom ion, cobalt ion, nickel ion, palladium
Ion, sulfite, hydroxylamine, hydrazine
Other than -SH, SO_ThreeH, -NHNH_Two, -CO
Compounds containing a group such as CH (OH)-are exemplified. Specific examples of such a reducing substance include:
Is ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanol
, Diethanolamine, N, N-dimethylaniline, hydride
Razine, ethyl mercaptan, benzenesulfonic acid, p-
And toluene sulfonic acid. The above-mentioned reducing substance is the same as that of the above-mentioned ethylene polymerization.
To 100 parts by weight of the copolymer or ethylene copolymer
Is 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight
Used in quantity. The graft modification of the ethylene (co) polymer is carried out by
It can be performed by a conventionally known method, for example, ethylene
Dissolve the (co) olefin copolymer in an organic solvent and then
Polar monomers and radical initiators are added to the solution,
At a temperature of 70-200C, preferably 80-190C,
The reaction is performed for 0.5 to 15 hours, preferably 1 to 10 hours.
This is done by: Graft modification of ethylene (co) polymer
The organic solvent used at this time dissolves ethylene (co) polymer.
It can be used without particular limitation as long as it is a solvable organic solvent.
Can be Examples of such an organic solvent include benzene,
Aromatic hydrocarbon solvents such as toluene and xylene, pens
Aliphatic hydrocarbon solvents such as tan, hexane and heptane
And the like. Also, using an extruder or the like, without solvent,
Ethylene / α-olefin copolymer and polar monomer
React to form a graft-modified ethylene / α-olefin
Polymers can be produced. The reaction temperature is usually
Above the melting point of the ren / α-olefin copolymer, specifically
It is in the range of 120-250 ° C. Under such temperature conditions
Is usually 0.5 to 10 minutes. The thus obtained graft-modified
Derived from polar monomers in Tylene (co) polymer
The grafting amount of the grafting group is usually 0.1 to 50
%, Preferably in the range from 0.3 to 30% by weight. [Ethylene-based copolymer composition]
The tylene-based copolymer composition is the [I] ethylene • α-
Olefin copolymer and [II] graft-modified ethylene
(I) ethylene-α-olefin
And [II] graft-modified ethylene (co) polymer
The weight ratio with the coalescence ([I]: [II]) is 99.5: 0.5-0.5
60:40, preferably in the range of 99: 1 to 70:30
Desirably. 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 antioxidant, hydrochloric acid absorbent and antioxidant are required
May be blended according to. The ethylene copolymer composition of the present invention is
It can be manufactured using known methods, for example,
It can be manufactured by the following method. (1) Ethylene / α-olefin copolymer composition [I]
And a graft-modified ethylene (co) polymer [II], and
Extruder, kneader, etc.
Method of mechanically blending using (2) Ethylene / α-olefin copolymer
Composition [I] and graft-modified ethylene (co) polymer
[II] and other components added as desired
Solvents (eg; hexane, heptane, decane, cyclohexane
Carbonization of xane, benzene, toluene and xylene
A hydrogen solvent) and then removing the solvent. (3) Ethylene / α-olefin copolymer
Composition [I] and graft-modified ethylene (co) polymer
[II] and other components added as desired
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 prepared by ordinary press molding.
Shape, air-cooled inflation molding, air-cooled two-stage cooling inflation
Solution molding, high-speed inflation molding, T-dif
Processing by film molding, water-cooled inflation molding, etc.
Thereby, a film can be obtained. in this way
The film formed by molding has excellent transparency and mechanical strength.
Heat sealability and e
Has good tackiness, heat resistance, good blocking properties, etc.
I have. Also, the composition of the ethylene / α-olefin copolymer
Because the distribution is extremely narrow, there is no stickiness on the film surface.
No. In addition, high-speed extrusion is possible due to low stress even in high shear range.
Power consumption and low power consumption.
is there. Molding the ethylene copolymer composition of the present invention
The resulting film is a standard bag, sugar bag,
Various packaging films, such as oil-based packaging bags and water-based packaging bags, and agricultural products
It is suitable for industrial materials. Also, nylon, polyes
These have excellent adhesion to tellurium, metal foil, etc.
To be used as a multilayer film
You can also. [0174] As described above, the ethylene copolymer composition of the present invention comprises:
With a narrow composition distribution, good thermal stability, and excellent moldability
Tylene / α-olefin copolymer [A] and ethylene
Ethylene / α- consisting of α-olefin copolymer [B]
Olefin copolymer composition [I] and graft-modified ethylene
Melt tension due to blending of (co) polymer [II]
High formability and low stress in the high shear area
You. From such an ethylene copolymer composition, a transparent
Film with excellent adhesion and excellent adhesion to highly polar materials
Can be manufactured. [0175] 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 (cloudiness)] Press sheet of 0.5 mm thickness
And measured according to ASTM-D-1003-61. However,
To remove the influence of the sheet surface on the set value,
Immerse the press sheet in a quartz optical cell filled with alcohol.
The haze, that is, the internal haze was measured in the immersed state. [Measurement method of adhesive strength] Modified polyethylene having a thickness of 100 µ
Using a press sheet of a composition containing
After performing the body and heat sealing, measure the peel strength.
And the adhesive strength was evaluated. The thickness is 0.
5mm aluminum foil and 1.0mm thick 6-nylo
Sheet was used. Heat between press sheet and adherend
The seal is 200 ℃, 1kg using a heat sealer.
/ Cm^TwoFor 60 seconds. Heat sealed
Then, cut out a test piece of 25 mm width and 150 mm length,
The adherend foil layer is 200 m in the 180 ° direction with respect to the composition layer.
By peeling at a peel speed of m / min, adhesion between two layers
The strength was measured. [0177] [Production Example 1] [Polymerization of ethylene / α-olefin 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) 28.
7 liters were added dropwise over one hour. At this time, the temperature in the system
It was kept at 0 ° C. Continue to react at 0 ° C for 30 minutes, then
Raise the temperature to 95 ° C over 1.5 hours and at that temperature for 20 hours
Reaction. Thereafter, the temperature was lowered to 60 ° C, and the supernatant was decanted.
It was removed by the tation 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) 6.6 liters
And bis (1.3-dimethylcyclopentadienyl) zirco
Solution of toluene dichloride (Zr; 28.1 mm
2.0 liters at 80 ° C for 30 minutes
Then, the mixture was further reacted at 80 ° C. for 2 hours. afterwards,
By removing the supernatant and washing twice with hexane,
Solid catalyst containing 3.6 mg zirconium per gram
I got [Preparation of Preliminary Polymerization Catalyst]
85 liter hex containing isobutylaluminum
To Sun, 0.85 kg of the solid catalyst obtained above and 1-
255 g of hexene was added, and ethylene was added at 35 ° C. for 12 hours.
By performing pre-polymerization, 10 g of solid catalyst per 1 g
A prepolymerized catalyst in which polyethylene was prepolymerized was obtained. This
[Η] of the ethylene polymer was 1.74 dl / g.
Was. [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
The prepolymerized catalyst was 0.18 mmole in terms of zirconium atoms.
/ 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 =
0.032, hydrogen / ethylene = 4.5 × 10^-Four,ethylene
Concentration = 25%). The ethylene / 1-hexene thus obtained
The yield of the styrene copolymer (A-1) was 6.3 kg / h.
Has an MFR of 0.40 g / 10 min and a density of 0.90 g
8g / cm^ThreeAnd the decane-soluble portion at room temperature is 0.5
It was 4 wt%. [0182] [Production Example 2] [Production of modified polyethylene] Toluene was used as a reaction solvent.
750 g of toluene per 5.7 liters
Polyethylene (polymerization of ethylene with a commercially available Ti catalyst
Things. Density = 0.965 g / cm^Three, MFR = 15.0
g / 10 min) at 160 ° C. Next, the solution of maleic anhydride was added to this solution.
Ene solution (44.1 g / 250 ml) and dicumylpe
Solution (3.6 g / 50) of toluene (DCP) in toluene
ml) was gradually fed from a separate conduit over 4 hours. After the end of the supply, the reaction was continued at 160 ° C. for 30 minutes.
And then cooled to room temperature to precipitate the polymer.
Was. Filter the precipitated polymer and repeat with acetone.
Return washing, drying under reduced pressure at 80 ° C all day and night
The functional polyethylene (C-1) was obtained. Elemental analysis was performed on the modified polyethylene.
When the graft amount of maleic anhydride was measured,
No equivalent of 2.3 g per 100 g of modified polyethylene
It was found that water maleic acid was graft-polymerized.
The density of this modified polyethylene is 0.965 g / c.
m^Three, MFR was 4.1 g / 10 min. [0186] Example 1 Ethylene / 1-hexene obtained in Production Example 1
Copolymer (A-1) (density 0.908 g / cm^Three, MFR
0.40 g / 10 min) and the density and MFR are shown in Table 1.
Except that the adjustment was performed as described above.
Tylene / 1-hexene copolymer (B-1) and Production Example 2
The modified polyethylene (C-1) obtained in (A-1)
/ (B-1) / (C-1) = 57/38/5
Dry blend and then add 100 parts by weight of resin
Tri (2,4-di-t-butylphenyl) as secondary antioxidant
0.05% by weight of phosphate, n as heat stabilizer
-Octadecyl-3- (4'hydroxy-3 ', 5'-di-t-butylphenyl
0.1% by weight of propenylate as hydrochloric acid absorbent
Of 0.05% by weight of calcium stearate.
After that, use a conical tapered twin-screw extruder manufactured by Haake.
Used, kneaded at a set temperature of 180 ° C, ethylene copolymer
A composition was obtained. The density of the obtained ethylene copolymer composition
Is 0.924 g / cm^ThreeAnd the MFR is 2.0 g / 10
Minutes. The results are shown in Table 2. [Press sheet molding] 200 ° C. using a press molding machine
And pellets of the ethylene-based copolymer composition for 10 minutes.
Heated. Then, 100kg / cm^TwoHold for 3 minutes under pressure
After pressing, set the pressure to 10 with a cooling press set at 20 ° C.
0kg / cm^TwoPress sheet for 5 minutes
Made. The transparency of the obtained press sheet, aluminum
Characteristics such as adhesion strength to aluminum foil or 6-nylon sheet.
The properties were measured. The results are shown in Table 2. Table 2 shows the results.
This composition has good transparency and melt tension.
Excellent moldability due to high fluidity index
And more polar like aluminum or nylon
It can be seen that the adhesive strength with the material is excellent. [0189] [Table 1][0190] [Table 2]

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiyuki Tsutsui 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-4-305447 (JP) JP-A-60-35007 (JP, A) JP-A-60-35006 (JP, A) JP-A-62-121709 (JP, A) JP-A-62-119214 (JP, A) 59-43042 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08F 4/64-4/69

Claims (1)

(57) [Claim 1] [I] A transition metal belonging to Group IV of the periodic table containing (a) an organoaluminum oxy compound and (b) a ligand having a cyclopentadienyl skeleton And ethylene in the presence of an olefin polymerization catalyst containing the compound.
Obtained by copolymerizing α-olefin of
(A-i) Density is in the range of 0.850 to 0.980 g / cm ³ , (A-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.4 to 8 dl / g. Ethylene
α-olefin copolymer [A] 20 to 90% by weight,
(A) Organic aluminum oxy compound and (b) Periodic Table IV containing a ligand having a cyclopentadienyl skeleton
And an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a group III transition metal compound, and having a (B-i) density of 0.1.
850-0.980 g / cm ³ , (B-ii)
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.
Ethylene-α-olefin copolymer [B] in the range of 4 to 8 dl / g;
An olefin copolymer composition (however, the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B] are not the same); and [II] a graft-modified ethylene polymer or graft-modified A weight ratio of the [I] ethylene / α-olefin copolymer composition and the [II] graft-modified ethylene polymer or graft-modified ethylene copolymer ([I]: [I
(I)) is in the range of 99.5: 0.5 to 60:40.