JP3455767B2 - Graft-modified ethylene / α-olefin copolymer composition and ethylene-based copolymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a graft-modified ethylene
The present invention relates to an α-olefin copolymer composition and an ethylene-based copolymer composition containing the copolymer composition, more specifically, in comparison with a conventionally known ethylene-based copolymer or an ethylene-based copolymer composition. The present invention relates to a graft-modified ethylene / α-olefin copolymer composition and an ethylene-based copolymer composition capable of producing a film having excellent transparency, having good moldability, and having excellent adhesiveness with a metal or a polar resin. It is a thing.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when an inflation film is to be molded at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform a stable high speed molding, the melt tension (melt tension) of the ethylene-based copolymer should be considered for its molecular weight. You have to choose the bigger one. Similar properties are needed to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer at the time of extrusion at a high shear rate is small from the viewpoint of economic improvement such as quality improvement of the molded article and reduction of power consumption at the time of molding.

By the way, a method of improving the moldability by improving the melt tension (melt tension) and the expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in 56-90810
Japanese Patent Laid-Open No. 60-106806 and the like. However, ethylene-based polymers generally obtained by using a titanium-based catalyst, especially low-density ethylene-based copolymers, have a wide composition distribution, and there is a problem that molded products such as films are sticky.

Further, among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts have a relatively high melt tension but are inferior in thermal stability. There is. It is considered that this is because the chain end of the ethylene polymer produced using the chromium catalyst is likely to be an unsaturated bond.

Among the Ziegler type catalyst systems, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded product such as a film is less sticky. However, for example, in JP-A-60-35007, an ethylene-based polymer obtained by using a zirconocene compound containing a cyclopentadienyl derivative as a ligand as a catalyst has one terminal unsaturated bond per molecule. It is described that it contains, and like the ethylene polymer obtained by using the chromium catalyst, the thermal stability is expected to be poor. Further, since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Further, the ethylene-based copolymer generally does not have a polar group in the molecule and is essentially nonpolar, so that the adhesiveness to a highly polar material such as a metal or a polar resin is insufficient. . Therefore, when used by bonding with a highly polar material, it is necessary to subject the surface of the ethylene-based copolymer to flame treatment, corona discharge treatment, or primer treatment, which makes the operation complicated. .

For this reason, if the ethylene copolymer or ethylene copolymer has a high melt tension, an excellent fluidity, a good thermal stability, an excellent mechanical strength and an excellent adhesiveness with a highly polar material. When a polymer composition appears, its industrial value is extremely high.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has good thermal stability, excellent moldability, excellent transparency, and adhesiveness to a highly polar material. It is an object of the present invention to provide a graft-modified ethylene / α-olefin copolymer composition capable of producing a favorable film and an ethylene-based copolymer composition containing the copolymer composition.

[0009]

SUMMARY OF THE INVENTION Graft-modified ethylene / α according to the present invention
-The olefin copolymer composition contains [A] (a) an organoaluminum oxy compound and (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. Ethylene and α-C3-20 in the presence of olefin polymerization catalysts
Obtained by copolymerizing with an olefin, (A-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (A-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. A transition metal of Group IV of the periodic table containing 20 to 90% by weight of α-olefin copolymer, [B] (a) an organoaluminum oxy compound, and (b) a ligand having a cyclopentadienyl skeleton. In the presence of an olefin polymerization catalyst containing a compound and ethylene and α-C3-20
Obtained by copolymerizing with an olefin, (B-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (B-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. An ethylene / α-olefin copolymer composition comprising 10 to 80% by weight of an α-olefin copolymer (provided that ethylene /
The α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B] are not the same) and a polar monomer is graft-copolymerized.

The ethylene copolymer composition of the present invention comprises the above-mentioned [I] graft-modified ethylene / α-olefin copolymer composition and [II] polyolefin, and comprises the above-mentioned [I] graft-modified ethylene / α-olefin. The weight ratio ([I]: [II]) of the olefin copolymer composition to the [II] polyolefin is in the range of 1:99 to 99: 1.

The graft-modified ethylene / α-olefin copolymer composition and the ethylene-based copolymer composition containing the copolymer are excellent in thermal stability and moldability,
In addition, it is possible to produce a film having excellent transparency and excellent adhesiveness to a highly polar material.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The graft-modified ethylene / α-olefin copolymer composition and ethylene-based copolymer composition according to the present invention will be specifically described below.

Graft-modified ethylene / α-according to the present invention
The olefin copolymer composition is an ethylene / α-olefin copolymer composition comprising an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B] as described below, The polar monomer is graft copolymerized.

[Ethylene / α-olefin copolymer [A]] The ethylene / α-olefin copolymer [A] forming the ethylene / α-olefin copolymer composition is composed of ethylene and 3 to 20 carbon atoms. It is a random copolymer with α-olefin. Examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene and 1-
Examples include butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

Ethylene / α-olefin copolymer [A]
Then, the structural unit derived from ethylene is 50 to 100.
%, Preferably 55-99% by weight, more preferably 65-98% by weight, most preferably 70-96% by weight, with 0 to 3 constituent units derived from the α-olefin having 3 to 20 carbon atoms. It is desirable to be present in an amount of -50 wt%, preferably 1-45 wt%, more preferably 2-35 wt%, most preferably 4-30 wt%.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at the measurement temperature. 120
℃, measurement frequency 25.05MHz, spectrum width 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of.

Such an ethylene / α-olefin copolymer [A] preferably has the following characteristics (A-i) and (A-ii). ) ~ (Av
It is more preferable to have the characteristics shown in i), and it is particularly preferable to have the characteristics shown in the following (A-i) to (A-viii).

(A-i) The density (d) is 0.850 to 0.9.
80 g / cm ³ , preferably 0.880 to 0.940 g /
cm ³ , more preferably 0.890 to 0.935 g / c
m ³ , most preferably in the range of 0.900 to 0.930 g / cm ³ .

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

(A-ii) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 1.25.
It is desirable to be in the range of ˜8 dl / g, more preferably 1.27 to 6 dl / g.

(A-iii) The melt tension (MT (g)) and melt flow rate (MFR) at 190 ° C. are MT> 2.2 × MFR ^−0.84, preferably 8.0 × MFR ^−0.84 >MT> 2. it is desirable to preferably from .3 × MFR ^-0.84 satisfy the relationship represented by ^{7.5 × MFR -0.84>MT> 2.5} × MFR -0.84.

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

The melt flow rate (MFR) is AST
Measured under the conditions of 190 ° C. and 2.16 kg load according to M D1238-65T. (A-iv) The stress at 190 ℃ is 2.4 × 10 ⁶ dyne /
Flow index (FI (1 / sec)) and melt flow rate (MF), which are defined by shear rate when reaching cm ²
R) and FI <150 × MFR, preferably FI <140 × MFR, and more preferably FI <130 × MFR.

The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using a sample similar to MT measurement, manufactured by Toyo Seiki Seisakusho,
It is measured with a capillary flow characteristic tester at a resin temperature of 190 ° C. and a shear stress range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

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

(A-v) Molecular weight distribution (M
w / Mn, where Mw: weight average molecular weight, Mn: number average molecular weight) is preferably in the range of 1.5 to 4. The molecular weight distribution (Mw / Mn) is GPC manufactured by Millipore.
It measured using -150C as follows.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
T (Takeda Yakuhin) 0.025% by weight was used, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. . Standard polystyrene has a molecular weight of Mw <10
00 and Mw> 4 × 10 ⁶ were manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ were manufactured by Pressure Chemicals.

(A-vi) MT / (Mw / Mn) and FI / M
FR is MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (provided that the value of 0.03 × FI / MFR-3.0 is 0 when it is less than 0). 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 0 when it is less than 0), more preferably 0.03 × FI / MFR + 0.8. > MT / (Mw / Mn)
> 0.03 × FI / MFR-2.5 (where the value of 0.03 × FI / MFR-2.5 is 0 when it is less than 0) is preferably satisfied.

Since the MT value increases as the Mw / Mn value increases, the MT / (Mw / Mn) index was used to reduce the influence of the Mw / Mn value on the MT value. Similarly, since the FI value increases with an increase in the MFR value, the FI / MFR index was used to reduce the influence of the MFR value on the FI value.

(A-vii) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.)) and the density (d) are represented by 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 meet the relationship.

The temperature (Tm (° C.)) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
Raise the temperature to 0 ° C and hold at 200 ° C for 5 minutes, then at 20 ° C
It can be obtained from the endothermic curve when the temperature is decreased to room temperature at the speed of 10 / min, and then the temperature is increased at 10 ° C./min. For the measurement, a DSC-7 type device manufactured by Perkin Elmer was used.

(A-viii) When the n-decane-soluble component amount fraction (W (wt%)) and the density (d) at room temperature are 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

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

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

Ethylene / α-having the above characteristics
The olefin copolymer [A] is an organoaluminum oxy compound (a) described below, (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (c) a carrier. Optionally, in the presence of (d) an olefin polymerization catalyst formed from an organoaluminum compound, preferably (a) an organoaluminumoxy compound described below and at least two (b) cyclopentadienyl skeletons. Ethylene and C 3 in the presence of a transition metal compound of Group IV of the periodic table containing a ligand, (c) a carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound. .About.20 .alpha.-olefin and the resulting copolymer has a density of 0.850 to 0.9.
It can be produced by copolymerizing so that the amount becomes 80 g / cm ³ .

[Ethylene / α-olefin Copolymer [B]] The ethylene / α-olefin copolymer [B] constituting the ethylene / α-olefin copolymer composition is composed of ethylene and 3 to 20 carbon atoms. It is a random copolymer with α-olefin. Examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene and 1-
Examples include butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

Ethylene / α-olefin copolymer [B]
Then, the structural unit derived from ethylene is 50 to 100.
%, Preferably 55-99% by weight, more preferably 65-98% by weight, most preferably 70-96% by weight, with 0 to 3 constituent units derived from the α-olefin having 3 to 20 carbon atoms. It is desirable to be present in an amount of -50 wt%, preferably 1-45 wt%, more preferably 2-35 wt%, most preferably 4-30 wt%.

The ethylene / α-olefin copolymer [B] as described above preferably has the following characteristics (B-i) and (B-ii). ) ~ (Bi
It is particularly preferable to have the characteristics shown in v).

(Bi) Density (d) is 0.850 to 0.9
80 g / cm ³ , preferably 0.910 to 0.960 g /
cm ³ , more preferably 0.915 to 0.955 g / c
m ^3, and most preferably is desirably in the range of 0.920~0.950g / cm ^3.

(B-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 0.4 to
1.25 dl / g, more preferably 0.5-1.23 dl / g
It is desirable to be in the range of.

(B-iii) The temperature (Tm (° C.)) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) and the density (d) are Tm <400 × d-250, preferably Tm. <450 × d-297 More preferably, Tm <500 × d-344, particularly preferably Tm <550 × d-391.

(B-iv) When the n-decane-soluble component amount fraction (W (wt%)) and the density (d) at room temperature are 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

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

Further, in the ethylene / α-olefin copolymer [B], the number of unsaturated bonds present in the molecule is not more than 0.5 per 1000 carbon atoms, and one per polymer molecule. It is desirable to be less than.

Ethylene / α-having the above characteristics
The olefin copolymer [B] includes (a) an organoaluminum oxy compound, (b) a transition metal compound, and
And (c) a carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound, in the presence of 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.
It can be produced by copolymerizing so as to have m ³ .

(A) Organoaluminumoxy which is a catalyst component used in the copolymerization of the ethylene / α-olefin copolymers [A] and [B] to form the ethylene / α-olefin copolymer composition below. The compound, (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, (c) a carrier and (d) an organoaluminum compound will be specifically described.

In the present invention, the organoaluminum oxy compound (a) used in the copolymerization of the ethylene / α-olefin copolymers [A] and [B] (hereinafter sometimes referred to as "component (a)"). ) May be a conventionally known benzene-soluble aluminoxane or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted.

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

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

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

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

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

Group IV of the periodic table containing (b) a ligand having a cyclopentadienyl skeleton used in the copolymerization of ethylene / α-olefin copolymers [A] and [B] in the present invention Transition metal compound (hereinafter “component (b)”)
May be described as. ) Is specifically a transition metal compound represented by the following general formula [b-I].

ML _x [b-I] [wherein M is a transition metal atom selected from Group IVB of the periodic table, L is a ligand coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and L 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. , SO ₃ R
A group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom, and x is a valence of the transition metal. ]

In the above general formula [b-I], M is a transition metal atom selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium,
Preferred is zirconium.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a trialkylsilyl group or a halogen atom.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [b-I] contains two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons among them are Alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups,
It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. A transition metal compound containing a ligand having such a cyclopentadienyl skeleton has, for example, when the valence of the transition metal is 4,
More specifically, it is represented by the following general formula [I ′].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [I '] (In the formula, M is the above transition metal atom, and R ² is a group (ligand) having a cyclopentadienyl skeleton. And R ³ ,
R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton,
Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group, halogen atom or hydrogen atom, k is an integer of 1 or more, and k + l + m + n = 4 is there. ) In the present invention, in the above general formula, R ² , R ³ , R ⁴
A metallocene compound in which two of R ⁵ and R ⁵ (for example, R ² and R ³ ) are groups (ligands) having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene groups. It may be connected via. Further, in this case, the other ligands (for example, R ⁴ and R ⁵ ) are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group. , SO ₃ R, a halogen atom or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethyl silylene bis (methylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

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

Periodic Table IV containing a ligand (b) having a cyclopentadienyl skeleton, which is used in the copolymerization of the ethylene / α-olefin copolymer [A] in the present invention.
Group transition metal compounds are represented by the following formula [b-II] or [b-II
It is preferably a transition metal compound represented by I].

ML ¹ _X ... [b-II] (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand coordinated to the transition metal atom M, At least two of these ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ML ² _X ... [b-III] (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ² is a ligand coordinated to the transition metal atom, and among these, The at least two ligands L ² are a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and a ligand L ² other than the substituted cyclopentadienyl group. Has 1 to 12 carbon atoms
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) Hereinafter, the transition metal compound represented by the general formula [b-II] or [b-III] will be described more specifically.

In the above formula [b-II], M is a transition metal atom selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium, preferably zirconium.

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

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

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

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

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

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

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

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

The halogen atom is fluorine, chlorine, bromine or iodine.

Examples of the transition metal compound represented by the general formula [b-II] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl). ) Zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propyl) Cyclopentadienyl) zirconium dichloride,
Bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclo) Pentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl)
Zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium diethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n -Butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl Chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride, and the like. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including. In the present invention,
In the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Among these transition metal compounds represented by the general formula [b-II], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (n-butylcyclopentadienyl) zirconium dichloride (1-Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

In the above general formula [b-III], M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

L ² is a ligand coordinated to the transition metal atom M, and at least two ligands L ² among them have only 2 to 5 substituents selected from a methyl group and an ethyl group.
And substituted cyclopentadienyl groups, each of which may be the same or different. The substituted cyclopentadienyl group is a substituted cyclopentadienyl group having two or more substituents, preferably a substituted cyclopentadienyl group having two to three substituents, and a disubstituted cyclopentadienyl group. An enyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.
In addition, each substituent may be the same or different.

In the above formula [b-III], the ligand L ² other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is the same as L ¹ in the above general formula [b-II]. 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.

Examples of the transition metal compound represented by the general formula [b-III] include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride and bis (methylethylcyclopenta). Dienyl) zirconium dichloride bis (dimethylethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis (dimethylcyclopentadienyl) zirconium methoxychloride,
Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium diethoxide, bis (dimethylcyclopentadienyl) zirconium methyl chloride, bis (Dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium phenyl chloride, bis (dimethylcyclo Pentadienyl) zirconium hydride chloride, and the like.
In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is 1,2,
Includes 3- and 1,2,4-substitutes. In the present invention, in the zirconium compound as described above, zirconium metal,
A transition metal compound substituted with titanium metal or hafnium metal can be used.

Among these transition metal compounds represented by the general formula [b-III], bis (1,3-dimethylcyclopentadienyl) zirconium dichloride and bis (1,3-
Diethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl)
Zirconium dichloride is especially preferred.

In the present invention, when producing the ethylene / α-olefin copolymer [A], at least one selected from the transition metal compounds represented by the above general formula [b-II] as the transition metal compound (b). And the above general formula [b-III]
It is preferable to use in combination with at least one selected from transition metal compounds represented by. In particular,
Bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in combination with bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propylmethylcyclopentadienyl) ) A combination of zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride Is preferred.

At least one transition metal compound selected from the transition metal compounds (b-II) represented by the general formula [b-II] and the transition metal compound represented by the general formula [b-III]. The at least one transition metal compound selected from (b-III) means a molar ratio (b-II / b-III) of 99/1 to
50/50, preferably 97/3 to 70/30, more preferably 95/5 to 75/25, most preferably 90 /
It is preferably used in such an amount that the range is 10 to 80/20.

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

In the present invention, the carrier (c) used in the copolymerization of the ethylene / α-olefin copolymers [A] and [B] (hereinafter sometimes referred to as "component (c)") is used. An inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 200 μm, in the form of granules or fine particles is used. Of these, porous oxides are preferable as the inorganic carrier, and specifically, Si is used.
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO _2, etc. or mixtures thereof, such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , Si
_{O 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -Cr 2 O 3, S
Examples thereof include iO ₂ —TiO ₂ —MgO. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Carbonate such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
It does not matter if it contains sulfates, nitrates or oxides.

Although the carrier (c) has different properties depending on its type and production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. , The pore volume is 0.3-
It is preferably 2.5 cm ³ / g. The carrier is, if necessary, 100 to 1000 ° C, preferably 150 to 70 ° C.
It is used after firing at 0 ° C.

In such carrier (c), it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl groups are 1.0% by weight or more, preferably 1.0% by weight. 5 to 4.0% by weight, particularly preferably 2.0 to 3.5
It is desirable that the content is wt%.

Here, the amount of water adsorbed on the carrier (c) (% by weight)
And the amount of surface hydroxyl groups (% by weight) is determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Surface hydroxyl group amount (% by weight) = {(X−Y) / X} × 100 Further, the carrier (c) that can be used in the present invention is an organic compound granule having a particle size of 10 to 300 μm. Examples thereof include solid or fine particle solids. These organic compounds include ethylene, propylene, 1-butene,
Examples of (co) polymers formed mainly from α-olefins having 2 to 14 carbon atoms such as 4-methyl-1-pentene, or polymers or copolymers formed mainly from vinylcyclohexane or styrene can do.

The catalyst used in the copolymerization of the ethylene / α-olefin copolymers [A] and [B] in the present invention is the above-mentioned (a) organoaluminum oxy compound, (b).
Formed from a transition metal compound and (c) a carrier,
If necessary, it may contain (d) an organoaluminum compound.

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

R ¹ _n AlX _3-n ... [IV] (In the formula [IV], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1
It is 3. ) In the above general formula [IV], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n- Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Such an organoaluminum compound (d)
Specifically, the following compounds may be mentioned. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, as the organoaluminum compound (d), a compound represented by the following general formula [V] can be used. R ¹ _n AlY _3-n ... [V] (In the formula [V], R ¹ is the same as above, and Y is —OR ²
Group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) Compounds represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like; (4) compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2
(5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ; (6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN
(Et) Al (iso-Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas [IV] and [V], the general formulas R ¹ ₃ Al and R ¹
_The compounds represented by _n Al (OR ² ) _3-n and R ¹ _n Al (OAlR ⁴ ₂ ) _3-n are preferable, and R is an isoalkyl group.
Compounds with n = 2 are preferred.

In the present invention, when the ethylene / α-olefin copolymers [A] and [B] are produced, the above-mentioned component (a), component (b) and component (c), and if necessary, A catalyst prepared by contacting the component (d) is used. At this time, the order of contacting the components (a) to (d) is arbitrarily selected, but the component (c) is preferable.
And component (a) are mixed and contacted, then component (b) is mixed and contacted, and further component (d) is mixed and contacted if necessary. When the component (b) is formed of two or more kinds of transition metal compounds, the two or more kinds of transition metal compounds forming the component (b) are mixed in advance and then mixed and contacted with other components. Is preferred.

The contact of the above components (a) to (d) can be carried out in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride , Halogenated hydrocarbons such as chlorobenzene and dichloromethane, or a mixture thereof.

Component (a), component (b) and component
(C), when the component (d) is mixed and contacted as necessary
The component (b) is usually 5 × 10 per 1 g of the component (c).^-6
~ 5 x 10 ^-FourMol, preferably 10^-Five~ 2 x 10^-FourMole
And the concentration of component (b) is about 10^-Four~ 2x
10^-2Mol / liter (solvent), preferably 2 × 10^-Four
-10^-2The range is mol / liter (solvent). component
Source of aluminum in (a) and transition metal in component (b)
Child ratio (Al / transition metal) is usually 10 to 500, preferably
20-200. Ingredients used as needed
Aluminum atom (Al-d) of (d) and component (a)
Atomic ratio of aluminum atoms (Al-a) (Al-d / Al-a)
Is usually in the range of 0.02 to 3, preferably 0.05 to 1.5.
It is a fence. Component (a), component (b) and component (c),
Mixing temperature when mixing and contacting the component (d) as necessary
Is usually -50 to 150 ° C, preferably -20 to 120.
And the contact time is 1 minute to 50 hours, preferably 10
Minutes to 25 hours.

Ethylene / α-obtained as described above
The catalyst used in the production of the olefin copolymer [A] and
And the catalyst (solid catalyst component) used in the production of [B] is
Transition metal atom derived from component (b) per 1 g of component (c)
Is 5 × 10^-6~ 5 x 10^-FourGram atom, preferably 10
^-Five~ 2 x 10^-FourSupported in the amount of gram atom, and also the component
(C) Derived from component (a) and component (d) per 1 g
10 aluminum atoms ^-3~ 5 x 10^-2Gram atom, good
2x10 is better^-3~ 2 x 10^-2Carried in the amount of gram atom
It is desirable that

Ethylene / α-olefin copolymer [A]
The catalyst used for the production of [B] and [B] is obtained by prepolymerizing an olefin in the presence of the above-mentioned component (a), component (b), component (c) and optionally component (d). It may be a prepolymerization catalyst. Prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned component (a), component (b) and component (c), and optionally in the coexistence of component (d). Can be done by. The solid catalyst component is preferably formed from the components (a) to (c). in this case,
In addition to the solid catalyst component, component (a) and / or component (d) may be further added.

The olefins used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1 -Octene, 1-decene, 1
Examples include -dodecene and 1-tetradecene. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

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

The prepolymerization catalyst is prepared, for example, as follows. That is, the carrier (component (c)) is suspended in inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to this suspension, and the mixture is reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon. A transition metal compound (component (b)) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduced therein to obtain a prepolymerization catalyst.

The amount of the olefin (co) polymer produced by the prepolymerization is 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g, per 1 g of the carrier (c). desirable. Further, in the prepolymerization catalyst, the component (b) is about 5 as transition metal atoms per 1 g of the carrier (c).
× 10 ^{-6 to} 5 × 10 ^-4 gram atom, preferably 10 ^-5 to
The aluminum atom (Al) derived from the component (a) and the component (d), which is supported in the amount of 2 × 10 ⁻⁴ gram atom, is
The molar ratio (Al / M) to the transition metal atom (M) derived from the component (a) is 5 to 200, preferably 10 to 15.
It is desirable that the amount is carried in the range of 0.

Preliminary polymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

The ethylene / α-olefin copolymers [A] and [B] used in the present invention are prepared by adding ethylene and an α-olefin having 3 to 20 carbon atoms, such as propylene, in the presence of the above catalyst. , 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
It is obtained by copolymerizing octadecene and 1-eicosene.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples include petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When carrying out the slurry polymerization method or the gas phase polymerization method, the catalyst as described above is usually used as the concentration of the transition metal atom in the polymerization reaction system in the range of 10 ^-8 to 10 ^-3 gram atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

Further, in the polymerization, in addition to the organoaluminum oxy compound (component (a)) and the organoaluminum compound (component (d)) supported on the carrier, the organoaluminum oxy compound and / or the organic aluminum oxy compound and / or the organic aluminum oxy compound not supported are further supported. An aluminum compound may be used. In this case, the atomic ratio of the aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and / or the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (b) (Al / M ) Is 5
~ 300, preferably 10-200, more preferably 1
It is in the range of 5-150.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C., and when carrying out the gas phase polymerization method, The polymerization temperature is usually 0 to 120 ° C., preferably 20.
Is in the range of -100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. [Ethylene / α-olefin Copolymer Composition] The ethylene / α-olefin copolymer composition is the above-mentioned ethylene / α-olefin copolymer composition.
It comprises an olefin copolymer [A] and an ethylene / α-olefin copolymer [B], and the ethylene / α-olefin copolymer [A] is 20 to 90% by weight, preferably 40%.
The amount of ethylene-α-olefin copolymer [B] is 10 to 80% by weight, preferably 25 to 75% by weight.
It is preferably included in an amount of 60% by weight. (However,
Ethylene / α-olefin copolymer [A] and ethylene /
(Not the same as α-olefin copolymer [B])

Ethylene / α-olefin copolymer [A]
And [B] have a ratio ([A] / [B]) of the density of the ethylene / α-olefin copolymer [A] to the density of the ethylene / α-olefin copolymer [B] is preferably 1
It is used in combination so as to be less than, more preferably 0.930 to 0.999.

It is preferable that such an ethylene / α-olefin copolymer composition has the following properties (i) to (vi). (I) density 0.850~0.980g / cm ^3, preferably 0.890~0.955g / cm ^3, and particularly preferably in the range range of 0.900~0.950g / cm ^3.

(Ii) The melt flow rate (MFR) of the composition at 190 ° C. under a load of 2.16 kg is 0.1 to
It is desirable that the range is 100 g / 10 minutes, preferably 0.2 to 50 g / 10 minutes.

(Iii) It is desirable that the melt tension (MT (g)) and the melt flow rate (MFR) at 190 ° C. satisfy the relationship of MT ≧ 2.2 × MFR ^−0.84 .

(Iv) Stress at 190 ° C. is 2.4 × 1
The flow index (FI (1 / sec)) and the melt flow rate (MFR) defined by the shear rate when reaching 0 ⁶ dyne / cm ² are as follows: FI> 100 × MFR, preferably FI> 130 × MFR It is preferable that the relationship represented by FI> 150 × MFR is satisfied.

(V) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.) and density (d) are expressed as Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550 × d-391. It is desirable that the relationship be satisfied.

(Vi) When the n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at room temperature are 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
It is desirable that the relationship shown in 0.88)) + 0.1 is satisfied.

Such an ethylene / α-olefin copolymer composition can be produced by a known method, for example, the following method. (1) The ethylene / α-olefin copolymer [A], the ethylene / α-olefin copolymer [B], and other components optionally added are mechanically blended using an extruder, a kneader, or the like. how to.

(2) an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B],
And optionally other ingredients added to a suitable good solvent (eg; hexane, heptane, decane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene and xylene)
The method of dissolving in, and then removing the solvent.

(3) Ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer [B],
And a method in which other components optionally added are separately dissolved in a suitable good solvent, and then mixed, and then the solvent is removed.

(4) A method in which the above methods (1) to (3) are combined. Furthermore, the ethylene-based copolymer composition of the present invention can be divided into two or more stages under different reaction conditions by using one or a plurality of polymerization vessels to obtain an ethylene / α-olefin copolymer [A]. And an ethylene / α-olefin copolymer [B] can be produced by copolymerizing the same. Further, a plurality of polymerization vessels are used, and the ethylene / α-olefin copolymer [A] and It can also be produced by copolymerizing an ethylene / α-olefin copolymer [B].

[[I] Graft-modified ethylene / α-olefin copolymer composition] The [I] graft-modified ethylene / α-olefin copolymer composition of the present invention is as described above in the presence of a radical initiator. It can be obtained by reacting an ethylene / α-olefin copolymer composition with a polar monomer as described below.

Examples of the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or its derivative, and a vinyl ester compound. , Vinyl chloride and the like.

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 2-hydroxy.
-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol (Meth) acrylic acid ester such as ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1- All, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate,
Examples thereof include glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group,
Examples of such compounds include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.

[0136]

[Chemical 1]

In the formula, R ¹ is a hydrogen atom, a methyl group or an ethyl group, R ² is a hydrogen atom, a C 1-12, preferably a C 1-8 alkyl group, a C 6-12,
It is preferably 6-8 cycloalkyl group. The above-mentioned alkyl group and cycloalkyl group may further have a substituent.

Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives of allylamine, methacrylamine, N-methylacrylamine, N, N-
Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide; Acrylamide derivatives such as acrylamide and N-methylacrylamide; Aminostyrenes such as p-aminostyrene; 6-Aminohexylsuccinimide, 2- Aminoethyl succinimide or the like is used.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and epoxy group in one molecule, and such an epoxy group-containing ethylenically unsaturated compound is Specifically, glycidyl acrylate, glycidyl methacrylate, and the like, maleic acid mono- and diglycidyl esters, fumaric acid mono- and diglycidyl esters,
Mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, mono and glycidyl esters of itaconic acid, mono and diglycidyl esters of butenetricarboxylic acid, mono and diglycidyl esters of citraconic acid, endo-cis- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ) mono and diglycidyl esters,
Dicarboxylic acids such as mono- and diglycidyl esters of endo-cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ), mono- and glycidyl esters of allyl succinic acid Mono and alkyl glycidyl esters (alkyl group having 1 to 12 carbon atoms in the case of monoglycidyl ester), alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene,
3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene A monoxide etc. can be illustrated.

Examples of the aromatic vinyl compound include compounds represented by the following formula.

[0141]

[Chemical 2]

In the above formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group and an isopropyl group. Can be mentioned. R ³ represents a hydrocarbon group having 1 to ³ carbon atoms or a halogen atom, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. You can Also,
n usually represents an integer of 0 to 5, preferably 1 to 5.

Specific examples of such aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,
2-isopropenyl pyridine, 2-vinyl quinoline, 3-vinyl isoquinoline, N-vinyl carbazole, N-vinyl pyrrolidone etc. can be mentioned.

As the unsaturated carboxylic acid, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,
Unsaturated carboxylic acids such as 2,1] hept-2-ene-5,6-dicarboxylic acid, or their acid anhydrides or their derivatives (for example, acid halides, amides, imides, esters, etc.) can be mentioned. Specific examples of the compound include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -
Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid,
Maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferred.

Examples of vinyl ester compounds are vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, benzoic acid. Examples thereof include vinyl, vinyl pt-butylbenzoate, vinyl salicylate and vinyl cyclohexanecarboxylate.

The above-mentioned polar monomer is the above-mentioned ethylene / α-
It is generally used in an amount of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the olefin copolymer composition.

Examples of the radical initiator include organic peroxides and azo compounds. Specific examples of the organic peroxide 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-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valalate, benzoyl peroxide, t
-Butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide,
Examples thereof include m-toluyl peroxide.
Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

Such a radical initiator is generally preferably used in an amount of 0.001 to 10 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer composition.

The radical initiator is ethylene / α as it is.
The olefin copolymer composition and the polar monomer may be mixed and used, or the radical initiator may be dissolved in a small amount of an organic solvent and used. The organic solvent used here is not particularly limited as long as it is an organic solvent capable of dissolving the radical initiator. As such an organic solvent, benzene,
Aromatic hydrocarbon solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; Cyclohexane,
Alicyclic hydrocarbon-based solvents such as methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, alcohol solvents such as n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol;
Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether,
Mention may be made of ethereal solvents such as diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

In the present invention, a reducing substance may be used when the ethylene / α-olefin copolymer composition is graft-modified. The reducing substance has a function of improving the graft amount in the resulting graft-modified ethylene / α-olefin copolymer composition.

Examples of the reducing substance include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine and hydrazine, as well as —SH, SO ₃ H, —NHNH ₂ , CO
Examples include compounds containing groups such as CH (OH)-.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethyl mercaptan, benzenesulfonic acid, p-
Examples include toluene sulfonic acid.

The above-mentioned reducing substance is the above-mentioned ethylene / α
It is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the olefin copolymer composition.

Graft modification of the ethylene / α-olefin copolymer composition can be carried out by a conventionally known method,
For example, an ethylene / α-olefin copolymer composition is dissolved in an organic solvent, and then a polar monomer, a radical initiator and the like are added to the solution, and the temperature is 70 to 200 ° C., preferably 80.
At a temperature of ~ 190 ° C for 0.5 to 15 hours, preferably 1
It is carried out by reacting for 10 hours.

The organic solvent used for graft-modifying the ethylene / α-olefin copolymer composition is not particularly limited as long as it is an organic solvent capable of dissolving the ethylene / α-olefin copolymer composition. can do.

As such an organic solvent, benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

The graft amount of the graft group derived from the polar monomer in the graft-modified ethylene / α-olefin copolymer composition thus prepared is usually 0.1 to 50% by weight, preferably 0. .2 to 30% by weight
Is within the range of.

Also, using an extruder or the like, without solvent,
A graft-modified ethylene / α-olefin copolymer composition can be produced by reacting an ethylene / α-olefin copolymer composition with a polar monomer. The reaction temperature is usually at least the melting point of the ethylene / α-olefin copolymer composition, and specifically in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to
10 minutes.

The ethylene copolymer composition according to the present invention comprises the above-mentioned [I] graft-modified ethylene / α-olefin copolymer composition and the following [II] polyolefin. There is.

[[II] Polyolefin] The [II] polyolefin forming the ethylene-based copolymer composition according to the present invention is, for example, ethylene or a homopolymer of α-olefin having 3 to 20 carbon atoms, or ethylene and carbon. Number 3
It is a copolymer obtained from two or more kinds of monomers selected from .about.20 .alpha.-olefins.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, 2-methylbutene-1,3-methylbutene-1, hexene-1,3-methylpentene-1, 4-methylpentene-1,3,3-dimethylbutene-1,
Heptene-1, methylhexene-1, dimethylpentene-1,
Trimethylbutene-1, ethylpentene-1, octene-1,
Methylpentene-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-
1, diethylbutene-1, propylpentene-1, decene-
1, methylnonene-1, dimethyloctene, trimethylheptene-1, ethyloctene-1, methylethylheptene-
1, diethylhexene-1, dodecene-1, hexadodecene and the like can be mentioned.

[II] As the polyolefin, a homopolymer of ethylene or an α-olefin having 3 to 8 carbon atoms or a copolymer obtained from two or more kinds of monomers selected from ethylene and an α-olefin having 3 to 8 carbon atoms is used. It is preferably a polymer, and particularly preferably a copolymer of ethylene and propylene.

The [II] polyolefin forming the ethylene-based copolymer composition according to the present invention contains the repeating unit derived from the above ethylene or a C3-20α-olefin in an amount of usually 50 mol% or more, preferably 80 mol%
Above all, particularly preferably 100 mol% is contained.

The polyolefin [II] is derived from ethylene or a repeating unit derived from an α-olefin having 3 to 20 carbon atoms, or another compound capable of being polymerized with ethylene or an α-olefin having 3 to 20 carbon atoms. It may have a repeating unit.

Examples of such other compounds include chain polyene compounds, cyclic polyene compounds and cyclic monoene compounds. These polyene compounds are
A polyene having two or more conjugated or non-conjugated olefinic double bonds. Examples of such chain polyene compounds include 1,4-hexadiene, 1,5-hexadiene,
Mention may be made of 1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene and divinylbenzene.

In addition, as an example of the cyclic polyene compound,
1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-
Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene,
5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene- 5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene and the like can be mentioned.

Further examples of cyclic monoenes include monocycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene. ; Norbornene, 5-methyl
-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene,
Bicycloalkenes such as 5,5,6-trimethyl-2-norbornene and 2-bornene; 2,3,3a, 7a-tetrahydro-4,7-
Methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7
-Methano-1H-indene and other tricycloalkenes; 1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, as well as these compounds, 2-methyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 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-octahydronaphthalene, 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-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3, 4,4a, 5,
8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8
tetracycloalkenes such as a-octahydronaphthalene; hexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0 ^9.14 ] heptadecene-4, pentacyclo [8,8,1 ^2.9 , 1 ^4.7 , 1 ^11.18 ,
0,0 ^3.8 , 0 ^12.17 ] Heneicosen-5, octacyclo [8,
8,1 ^2.9, 1 ^4.7, 1 ^11.18, 0,0 ^3.8, can be exemplified 0 ^12.17] cyclic monoene compounds such as poly cycloalkene such docosenoic -5.

Further, the [II] polyolefin may include a structural unit derived from styrene or a substituted styrene.

In such a [II] polyolefin, 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is usually 0.4 to 7 dl / g, preferably 0.5 to 5 dl / g.

The [II] polyolefin forming the ethylene copolymer composition according to the present invention can be obtained by polymerizing or copolymerizing the above-mentioned α-olefin by a conventionally known method. This polymerization reaction is in the gas phase (gas phase method)
Can also be carried out in the liquid phase (liquid phase method).

[Ethylene Copolymer Composition] The ethylene copolymer composition of the present invention comprises the above [I] graft-modified ethylene / α-olefin copolymer composition and [II] polyolefin, [I] Graft-modified ethylene
The weight ratio ([I] / [II]) of the α-olefin copolymer composition to the [II] polyolefin is 1:99 to 99:
It is desirable that it is in the range of 1, preferably 2:98 to 98: 2.

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

The ethylene-based copolymer composition of the present invention can be produced by a known method, for example, the following method. (1) A method of mechanically blending the [I] graft-modified ethylene / α-olefin copolymer composition, the [II] polyolefin, and optionally other components with an extruder or a kneader.

(2) [I] Graft-modified ethylene / α-
An olefin copolymer composition and [II] a polyolefin,
And optionally other ingredients added to a suitable good solvent (eg; hexane, heptane, decane, cyclohexane,
A hydrocarbon solvent such as benzene, toluene and xylene), and then removing the solvent.

(3) [I] Graft-modified ethylene / α-
An olefin copolymer composition and [II] a polyolefin,
And a method in which other components optionally added are separately dissolved in a suitable good solvent, and then mixed, and then the solvent is removed.

(4) A method in which the above methods (1) to (3) are combined. The ethylene-based copolymer composition of the present invention is processed into a film by ordinary press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding and the like. Obtainable. The film formed in this way has transparency,
Excellent mechanical strength and blocking resistance, ordinary LLDP
It has heat sealability, hot tack property, heat resistance, etc. which are the characteristics of E. Further, since the composition distribution of the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B] is extremely narrow, the film surface is not sticky. Furthermore, since the stress is low even in the high shear region, high-speed extrusion is possible, power consumption is reduced, and it is economically advantageous.

The film obtained by processing the graft-modified ethylene / α-olefin copolymer composition and the ethylene copolymer composition of the present invention is a standard bag, a sugar bag, an oil packaging bag, or a water packaging. It is suitable for various packaging films such as bags and agricultural materials. Further, since it has excellent adhesiveness to nylon, polyester, metal foil, etc., it can be used as a multi-layer film by being bonded to these base materials.

[0178]

The graft-modified ethylene / α-olefin copolymer composition of the present invention has a high melt tension,
Since the stress in the high shear region is low, it has excellent moldability. From such a graft-modified ethylene / α-olefin copolymer composition, a film having excellent transparency and adhesion to a highly polar material can be produced.

The ethylene-based copolymer composition of the present invention comprises a graft-modified ethylene / α-olefin copolymer composition [I] having a small solid component, good thermal stability and excellent moldability, and a polyolefin. Since it is blended with [II], the melt tension is high and the stress in the high shear region is low, resulting in excellent moldability. From such an ethylene-based copolymer composition, a film having excellent transparency and adhesion to a highly polar material can be produced.

[0180]

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

In the present invention, the physical properties of the film were evaluated as follows. [Haze (Haze)] It was measured according to ASTM-D-1003-61 using a press sheet having a thickness of 0.5 mm. However, in order to remove the influence of the sheet surface on the measured value, the haze, that is, the internal haze was measured in a state where the press sheet was immersed in a quartz optical cell filled with benzyl alcohol.

[Measurement Method of Adhesive Strength] A press sheet of a modified copolymer having a thickness of 100 μm was used as a sample, heat-sealed with two kinds of adherends, and then the adhesive strength was measured by measuring the peel strength. evaluated. The thickness of the adherend is 0.5
mm aluminum foil and a 1.0 mm thick 6-nylon sheet were used. The heat sealing between the press sheet and the adherend is performed using a heat sealer at 200 ° C. and 1 kg /
It was performed under the conditions of cm ² and 60 seconds. After heat sealing,
A test piece with a width of 25 mm and a length of 150 mm is cut out, and the adherend foil layer is 200 m in 180 ° direction with respect to the modified polymer layer
By peeling at a peeling speed of m / min, the adhesive strength between the two layers was measured.

[0183]

[Production Example 1] [Polymerization of ethylene / α-olefin copolymer] [Preparation of catalyst component] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 liters of toluene and then cooled to 0 ° C. Cooled. Then, a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) 28.
7 liters were dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and reacted at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. To this system was added 6.6 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and bis (1.3-dimethylcyclopentadienyl) zirconium. 2.0 l of a toluene solution of dichloride (Zr; 28.1 mmol / l) was added dropwise at 80 ° C over 30 minutes, and further reacted at 80 ° C for 2 hours. afterwards,
By removing the supernatant and washing twice with hexane,
A solid catalyst was obtained containing 3.6 mg of zirconium per gram.

[Preparation of prepolymerized catalyst] 0.85 kg of the solid catalyst obtained above and 1-85% of hexane containing 1.7 mol of triisobutylaluminum were added.
Hexene (255 g) was added and ethylene was prepolymerized at 35 ° C. for 12 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The [η] of this ethylene polymer was 1.74 dl / g.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 70 ° C. The prepolymerized catalyst prepared above was converted into zirconium atoms at 0.18 mmol / h and triisobutylaluminum at 10 mmol / h.
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.032, hydrogen / ethylene = 4.5 × 10 ⁻⁴ , ethylene concentration = 25%).

The thus obtained ethylene / 1-hexene copolymer had a yield of 6.3 kg / h, an MFR of 0.40 g / 10 min and a density of 0.908 g / cm ^3.
The decane-soluble part at room temperature was 0.54 wt%.

[Preparation of Composition] The ethylene / 1-hexene copolymer (A-1) obtained in Production Example 1 (density: 0.908)
g / cm ³ , MFR 0.40 g / 10 min), density, MF
An ethylene / 1-hexene copolymer (B- was produced in the same manner as in Production Example 1 except that R was adjusted as shown in Table 1.
1) and (A-1) / (B-1) = 6/4 were dry-blended, and 100 parts by weight of the resin was further blended with tri (2,4-di) as a secondary antioxidant. 0.05% by weight of -t-butylphenyl) phosphate, n- as a heat stabilizer
Octadecyl-3- (4'hydroxy-3 ', 5'-di-t-butylphenyl) propinate was added in an amount of 0.1% by weight and calcium stearate as a hydrochloric acid absorbent was added in an amount of 0.05% by weight. Then, using a conical taper twin-screw extruder manufactured by Haake Co., Ltd., the mixture was kneaded at a set temperature of 180 ° C. to obtain an ethylene / α-olefin copolymer composition.

The obtained ethylene / α-olefin copolymerization
The density of the body composition is 0.922 g / cm ³And MFR is
It was 1.9 g / 10 minutes. Results of evaluation of other physical properties
The results are shown in Table 2.

[0190]

Example 1 Toluene was used as a reaction solvent, and 825 g of the ethylene / α-olefin copolymer composition per 5.7 liters of this toluene (the ethylene / α-olefin copolymer composition obtained in Production Example 1 above) was used. , Density = 0.922g
/ Cm ³ , MFR = 1.9 g / 10 min) was dissolved at 160 ° C.

Then, a toluene solution of maleic anhydride (4.13 g / 250 ml) and a toluene solution of dicumyl peroxide (DCP) (0.33 g / 5) were added to this solution.
0 ml) was gradually fed from a separate conduit over 4 hours.

After the end of the supply, the reaction was further continued at 160 ° C. for 30 minutes and then cooled to room temperature to precipitate a polymer. The precipitated polymer is filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C for a whole day and night to obtain the desired modified ethylene / α-olefin copolymer composition (C-1).
Got

Elemental analysis was conducted on the modified ethylene / α-olefin copolymer composition (C-1) to measure the grafted amount of maleic anhydride.
It was found that 0.2 g of maleic anhydride corresponding to 100 g of the α-olefin copolymer composition was graft-polymerized. The modified ethylene / α-olefin copolymer composition had a density of 0.922 g / cm ³ and an MFR of 1.0 g / 10 minutes.

The modified ethylene / α-olefin copolymer composition (C-1) thus obtained was used to measure its properties such as melt property. The results are shown in Table 3. [Press sheet molding] Using a press molding machine, 200 ° C
The modified ethylene / α-olefin copolymer composition (C-1) was heated for 10 minutes. Then 100 kg / cm
After being held under a pressure of ² for 3 minutes, a cooling sheet set at 20 ° C. was held for 5 minutes under a pressure of 100 kg / cm ² to prepare a press sheet.

Properties such as transparency of the obtained pressed sheet and adhesive strength with an aluminum foil or a 6-nylon sheet were measured. The results are shown in Table 3. From Table 3, this modified ethylene / α-olefin copolymer composition has excellent transparency, a high melt tension and a high fluidity index, and thus is excellent in moldability, and has a high polarity like aluminum and nylon. It can be seen that the adhesive strength with the material is excellent.

[0196]

[Table 1]

[0197]

[Table 2]

[0198]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Toshiyuki Tsutsui, No. 1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP 62-89716 (JP) , A) JP 5-222138 (JP, A) JP 5-59132 (JP, A) JP 5-50557 (JP, A) JP 4-214710 (JP, A) JP 1-236259 (JP, A) JP-A-60-108412 (JP, A) JP-A-59-147008 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 255/00 -255/10

Claims (2)

(57) [Claims] 1. A catalyst for olefin polymerization comprising [A] (a) an organoaluminum oxy compound and (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. In the presence of ethylene and α-C3-20
Obtained by copolymerizing with an olefin, (A-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (A-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. A transition metal of Group IV of the periodic table containing 20 to 90% by weight of α-olefin copolymer, [B] (a) an organoaluminum oxy compound, and (b) a ligand having a cyclopentadienyl skeleton. In the presence of an olefin polymerization catalyst containing a compound and ethylene and α-C3-20
Obtained by copolymerizing with an olefin, (B-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (B-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. An ethylene / α-olefin copolymer composition comprising 10 to 80% by weight of an α-olefin copolymer (provided that ethylene /
Graft-modified ethylene / α-olefin characterized in that a polar monomer is graft-copolymerized to the α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B]) Copolymer composition. 2. A catalyst for olefin polymerization comprising [I] (a) an organoaluminum oxy compound and (b) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. In the presence of ethylene and α-C3-20
Obtained by copolymerizing with an olefin, (A-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (A-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. A transition metal of Group IV of the periodic table containing 20 to 90% by weight of α-olefin copolymer [A], (a) an organoaluminumoxy compound, and (b) a ligand having a cyclopentadienyl skeleton. In the presence of an olefin polymerization catalyst containing a compound and ethylene and α-C3-20
Obtained by copolymerizing with an olefin, (B-
i) Ethylene having a density in the range of 0.850 to 0.980 g / cm ³ and (B-ii) an intrinsic viscosity [η] measured in decalin of 135 ° C. in the range of 0.4 to 8 dl / g. An ethylene / α-olefin copolymer composition consisting of 10 to 80% by weight of α-olefin copolymer [B] (however, ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer (Not the same as the polymer [B]), a graft-modified ethylene / α-olefin copolymer composition obtained by graft-copolymerizing a polar monomer, and a [II] polyolefin. An ethylene-based copolymer characterized in that the weight ratio ([I]: [II]) of the ethylene / α-olefin copolymer composition to the [II] polyolefin is in the range of 1:99 to 99: 1. Polymer composition.