JP2002179855A - Ethylenic copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylenic copolymer composition having excellent moldability, with which a film having excellent mechanical strength can be produced. SOLUTION: This ethylenic copolymer composition comprises an ethylene/α- olefin copolymer having a density, a melt flow rate, a temperature at the maximum peak position of endothermic curve measured by DSC, a melt tension, a fluidity index and a decane soluble part at 23 deg.C in a specific range and a specific olefinic elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-based copolymer composition, and more particularly to an ethylene-based copolymer or an ethylene-based copolymer composition which has better mechanical strength than conventionally known ethylene-based copolymer compositions. The present invention relates to an ethylene copolymer composition capable of producing a film and having excellent moldability.

[0002]

BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The required properties of the ethylene copolymer differ depending on the molding method and application. For example, when trying to mold an inflation film at high speed, in order to stably perform high-speed molding without shaking or tearing of bubbles, select an ethylene copolymer that has a large melt tension for its molecular weight. Must. Similar properties are necessary to prevent sagging or tearing in blow molding or to minimize width loss in T-die molding. In addition, in such extrusion molding, it is necessary to reduce the stress of the ethylene-based copolymer under high shear during extrusion from the economical viewpoint of improving the quality of molded articles and reducing power consumption during molding.

A method of improving the moldability by improving the melt tension and expansion ratio (die-swell ratio) of an ethylene polymer obtained using a Ziegler catalyst, particularly a titanium catalyst, is disclosed in Japanese Patent Application Laid-Open No. 56-90810. And Japanese Patent Application Laid-Open No. Sho 60-106806. However, in general, an ethylene-based polymer, particularly a low-density ethylene-based copolymer, obtained using a titanium-based catalyst has a problem that the composition distribution is wide and a molded article such as a film is sticky.

Further, among ethylene polymers produced using a Ziegler type catalyst, an ethylene polymer obtained using a chromium catalyst has relatively high melt tension, but is inferior in thermal stability. There are disadvantages. This is probably because the chain ends of the ethylene polymer produced using the chromium-based catalyst tend to be unsaturated bonds.

[0005] Among the Ziegler type catalyst systems, it is known that an ethylene polymer obtained by using a metallocene catalyst system has advantages such as a narrow composition distribution and a molded product such as a film being less sticky. However, for example, JP-A-60-35007 describes that an ethylene-based polymer obtained by using a zirconocene compound composed of a cyclopentadienyl derivative as a catalyst contains one terminal unsaturated bond per molecule. In addition, it is expected that the thermal stability is poor as in the case of the ethylene polymer obtained using the chromium-based catalyst. In addition, since the molecular weight distribution is narrow, there is a concern that fluidity during extrusion molding is poor.

For this reason, if an ethylene polymer having excellent melt tension, low stress in a high shear region, good thermal stability, excellent mechanical strength, and a narrow composition distribution appears, the industrial use of the polymer is considered. The target value is extremely large.

The inventors of the present invention have conducted intensive studies in view of such circumstances, and have found that (a) a bidentate in which two groups selected from a specific indenyl group or a substituent thereof are bonded via a lower alkylene group. A compound of a transition metal of Group IVB of the periodic table having a ligand or a compound of a transition metal of Group IVB of the periodic table having a specific substituted cyclopentadienyl group as a ligand;
In the presence of an olefin polymerization catalyst formed from (b) an organoaluminum oxy compound, (c) a carrier, and if necessary (d) an organoaluminum compound, ethylene and an α-olefin having 3 to 20 carbon atoms are present. It has been found that an ethylene / α-olefin copolymer obtained by copolymerizing is excellent in melt tension and heat stability and has a narrow composition distribution. And, as a result of further study, an ethylene copolymer composition obtained by blending the above-mentioned ethylene / α-olefin copolymer with a specific olefin elastomer produces a film having excellent film impact. The present invention was found to be excellent in moldability and to complete the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ethylene copolymer composition capable of producing a film having excellent mechanical strength and having excellent moldability.

[0009]

SUMMARY OF THE INVENTION The ethylene copolymer composition according to the present invention comprises [A] (A-i) ethylene and α-C 3-20.
A copolymer with an olefin, wherein (A-ii) density (d)
Is in the range of 0.880 to 0.960 g / cm ³ , and (Ai
ii) The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.01 to 200 g / 10 min, and (A-iv) the maximum endothermic curve measured by a differential scanning calorimeter (DSC). Temperature at peak position (Tm (° C))
And the density (d) satisfy the relationship of Tm <400 × d−250, and (A−v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR)
^Satisfies the relationship expressed by MT> 2.2 × MFR ^-0.84 , and (A-vi) 190 of the molten polymer
The flow index (FI (1)) defined by the shear rate when the stress at 2.4 ° C. reaches 2.4 × 10 ⁶ dyne / cm ²
/ Sec)) and melt flow rate (MFR) satisfy the relationship of FI> 75 × MFR, (A-vii) Decane-soluble portion (W (% by weight)) at 23 ° C. and density (d) Is MFR ≦
When 10 g / 10 min, W <80 × exp (−100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp (−100 (D-
0.88)) + 0.1% by weight of an ethylene / α-olefin copolymer satisfying the relationship of 0.1, and [B] (Bi) the density (d) is 0.990 g / cm ³ or less. ,
(B-ii) 1 to 40% by weight of an olefin elastomer having a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg within a range of 0.01 to 100 g / 10 minutes.
Wherein the ratio ([B] / [A]) of the density of the [B] olefin-based elastomer to the density of the [A] ethylene / α-olefin copolymer is less than 1. I have.

[0010] Such an ethylene copolymer can produce a film having excellent mechanical strength and has excellent moldability.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the ethylene copolymer composition according to the present invention will be specifically described. The ethylene copolymer composition according to the present invention comprises an ethylene / α-olefin copolymer [A] and an olefin elastomer [B].

[Ethylene / α-olefin copolymer [A]] The ethylene / α-olefin copolymer [A] constituting the ethylene-based copolymer composition according to the present invention is composed of ethylene and C3-C20. Is a random copolymer with α-olefin. Examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0013] Ethylene / α-olefin copolymer [A]
In the above, the constituent unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7 to 99% by weight.
The structural unit derived from the α-olefin having 3 to 20 carbon atoms is present in an amount of 0 to 96% by weight, and 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight.
Is desirably present.

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

Such an ethylene / α-olefin copolymer [A] has the following properties (A-ii) to (A-vii). (A-ii) Density (d) is 0.880 to 0.960 g / cm
³ , but preferably 0.890 to 0.935 g.
/ Cm ³ , more preferably 0.905 to 0.930 g / c
It is desirably in the range of m ³ .

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

(A-iii) Melt flow rate (MFR)
Is in the range of 0.01 to 200 g / 10 min, preferably 0.05 to 50 g / 10 min, more preferably 0.1.
It is desirably in the range of 10 to 10 g / 10 minutes.

The melt flow rate (MFR) is
It is measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238-65T. (A-iv) The temperature (Tm (° C.)) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are as follows: It is desirable to satisfy the relationship shown by.

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(° C)) is about 10 mg /
The temperature is raised to 200 ° C. per minute, the temperature is kept at 200 ° C. for 5 minutes, the temperature is lowered to room temperature at 20 ° C./min, and then the temperature is raised at 10 ° C./min. The measurement was carried out using a DSC-7 type device manufactured by PerkinElmer.

(Av) Melt tension at 190 ° C. (MT
(G)) and the melt flow rate (MFR) satisfy the relationship expressed as MT> 2.2 × MFR− ^0.84 .

The ethylene / α-olefin copolymer [A] according to the present invention has a high melt tension (MT) and good moldability. The melt tension (MT
(G)) is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is,
The produced polymer powder is melted by a usual method and then pelletized to prepare a measurement sample. Using an MT measuring device manufactured by Toyo Seiki Seisaku-sho, resin temperature 190 ° C., extrusion speed 15 mm / min, winding speed 10-20 m / min, nozzle Diameter 2.09mmφ,
The test was performed under the condition of a nozzle length of 8 mm. When pelletizing,
0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n- as a heat stabilizer were added to the ethylene / α-olefin copolymer [A] in advance. 0.1% by weight of octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were blended.

(A-vi) Stress at 190 ° C. is 2.4 ×
The flow index (FI (1 / second)) defined by the shear rate when reaching 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are: It is desirable to satisfy the relationship shown by.

An ethylene / α-olefin copolymer [A] in which FI and MFR satisfy the above relationship.
Since a low stress is maintained up to a high shear rate, the processing torque is small and the formability is good.

The flow index (FI) is defined as the shear rate at which the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² . The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate, and measuring the stress at that time. That is, using the same sample as in the MT measurement, using a capillary flow characteristic tester manufactured by Toyo Seiki Seisaku-sho, the resin temperature was 190 ° C., and the shear stress range was 5 × 10 ^{4 to} 3 × 10 ⁶ dyn.
It is measured at about e / cm ² .

The MFR of the resin to be measured (g / 10 minutes)
The measurement is performed by changing the diameter of the nozzle as follows. 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-vii) When the fraction of the n-decane soluble component at room temperature (W (% by weight)) and the density (d) are MFR ≦ 10 g / 10 minutes, W <80 × exp (− 100 (d−0.88)) + 0.1 preferably W <60 × exp (−100 (d−0.88)) + 0.1, more preferably W <40 × exp (−100 (d−0.88) )) + 0.1 When MFR> 10 g / 10 minutes, the relationship represented by W <80 × (MFR-9) ^0.26 × exp (−100 (d−0.88)) + 0.1 is satisfied.

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

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

Further, the ethylene / α-olefin copolymer [A] has an unsaturated bond present in the molecule of not more than 0.5 per 1,000 carbon atoms, and one unsaturated bond per one molecule of the polymer. Desirably less than.

The quantification of the unsaturated bond was carried out by ¹³ C-NMR
Using the signal assigned to other than the double bond, ie, 10
The areal intensities of the signal in the range of ５０50 ppm and the signal attributed to the double bond, that is, the signal in the range of 105 to 150 ppm are determined from the integral curve and determined from the ratio.

Ethylene α-having the above-mentioned properties
The olefin copolymer [A] includes the following (a) a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier, and if necessary, (d) an olefin polymerization catalyst formed from an organoaluminum compound. In the presence, it can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms such that the obtained copolymer has a density of 0.880 to 0.960 g / cm ^3. .

The transition metal compound (a) (hereinafter sometimes referred to as “component (a)”) used in the present invention is a compound in which two groups selected from a specific indenyl group or a substituent thereof are lower. Group IVB transition metal compound having a bidentate ligand bonded via an alkylene group or a compound of a transition metal of Group IVB or a specific substituted cyclopentadienyl group as a ligand
The compound is a transition metal compound of Group IVB, specifically, a transition metal compound represented by the following formula [I] or [II].

MKL ¹ _X-2 ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the periodic table, and K and L ¹ are ligands coordinated to the transition metal atom. The ligand K is a bidentate ligand in which the same or different indenyl group, substituted indenyl group or a partial water additive thereof is bonded via a lower alkylene group,
The ligand L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is the valence of the transition metal atom M. ) ML ² _X ... [II] (In the formula [II], M is a transition metal selected from Group IVB of the periodic table, and L ² is a ligand coordinated to a transition metal atom. At least two ligands L
² is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group,
The ligand L ² other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X is a transition metal atom M Is the valence of In the above general formula [I], M is a transition metal atom selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.

K is a ligand coordinating to the transition metal atom, wherein the same or different indenyl group, substituted indenyl group, or a partial water additive of an indenyl group or a substituted indenyl group is bonded via a lower alkylene group. Is a bidentate ligand.

Specifically, an ethylenebisindenyl group, ethylenebis (4,5,6,7-tetrahydro-1-indenyl)
Group, ethylenebis (4-methyl-1-indenyl) group, ethylenebis (5-methyl-1-indenyl) group, ethylenebis (6-methyl-1-indenyl) group, ethylenebis (7-methyl-1- An indenyl) group.

L ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group,
Aryl groups, aralkyl groups and the like can be exemplified,
More specifically, a methyl group, an ethyl group, an n-propyl group,
Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group;
Examples thereof include cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and neophyl group.

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

Examples of the aryloxy group include a phenoxy group. A halogen atom is fluorine,
Chlorine, bromine and iodine. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.

Examples of the transition metal compound represented by the general formula [I] include ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,5,
6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1- Indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium methoxychloride, ethylenebis (4-methyl-1-indenyl) zirconium ethoxychloride, Ethylenebis (4-methyl-1-indenyl) zirconium butoxycyclolide, ethylenebis (4-methyl-1-indenyl) zirconium methoxide, ethylenebis (4-methyl-1-indenyl) zirconium methyl chloride, ethylenebis (4- Methyl-1-indenyl) zirconium dimethyl, Chirenbisu (4-methyl-1-indenyl) zirconium benzyl chloride, ethylene-bis (4-methyl-1-indenyl) zirconium dibenzyl, ethylenebis (4-methyl
1-indenyl) zirconium phenyl chloride, ethylenebis (4-methyl-1-indenyl) zirconium hydride chloride, and the like. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [I], ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,
5,6,7-Tetrahydro-1-indenyl) zirconium dichloride is particularly preferred.

In the above general formula [II], M is a number in the periodic table.
A transition metal atom selected from Group IVB, and specifically,
Zirconium, titanium or hafnium, preferably zirconium.

L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² have a substituent selected from a methyl group and an ethyl group of 2 to 5
Substituted cyclopentadienyl groups 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 is preferably 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.

[0043] In the above formula [II], the transition metal atom M ligand L ² other than the substituted cyclopentadienyl group coordinated to the general formula [I] L ¹ and similar to several carbons in 12 hydrocarbon groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups or hydrogen atoms.

Examples of the transition metal compound represented by the general formula [II] include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride, and bis (methylethylcyclopentadienyl). ) Zirconium dichloridebis (dimethylethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis (dimethylcyclopentadienyl) zirconium methoxychloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide , Bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium ethoxide, bis (dimethylcyclopentadiene) B) zirconium methyl chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium Phenyl chloride, bis (dimethylcyclopentadienyl) zirconium hydride chloride, and the like. In the above examples, the disubstituted cyclopentadienyl ring is
Includes 1,2- and 1,3-substituted, trisubstituted are 1,2,3- and
Including 1,2,4-substituted products. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [II], bis (1.3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride is particularly preferred.

Next, the organic aluminum oxy compound (b) will be described. The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) used in the present invention may be a conventionally known benzene-soluble aluminoxane. 27
It may be a benzene-insoluble organic aluminum oxy compound as disclosed in JP-A-6807.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly allowed to act on water, ice or steam in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover as a hydrocarbon solution.

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

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

Specific examples of the organoaluminum compound used in producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as tri-sec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

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

The organoaluminum compound as described above is
Used alone or in combination. Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrogen, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Hydrocarbon solvents such as chlorides, bromides and the like. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used.
Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is such that the organoaluminum oxy compound corresponding to 100 milligram atoms of Al is 10
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

The carrier (c) (hereinafter sometimes referred to as “component (c)”) used in the present invention is an inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 300 μm. A 200 μm granular or particulate solid is used. Of these, a porous oxide is preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, Ba
O, ThO ₂ or the like or a mixture thereof, for example, SiO _2-
MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂
-V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO
And the like. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

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 ,
Carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
Sulfate, nitrate and oxide components may be contained.

Such a carrier (c) has different properties depending on its kind and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. , Pore volume is 0.3 ~
Desirably, it is 2.5 cm ² / g. The carrier is optionally at 100 to 1000 ° C, preferably 150 to 70 ° C.
It is used after firing at 0 ° C.

Further, examples of the carrier (c) that can be used in the present invention include a granular or fine solid of an organic compound having a particle size of 10 to 300 μm. These organic compounds include those having 2 to 2 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
Produced mainly with 14 α-olefins (co)
Examples thereof include a polymer or a polymer or a copolymer formed mainly from vinylcyclohexane or styrene.

The catalyst used in the present invention is formed from the above-mentioned (a) a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier, and if necessary, (d)
An organic aluminum compound may be used.

As the (d) organoaluminum compound used as required (hereinafter sometimes referred to as “component (d)”), for example, an organoaluminum compound represented by the following general formula [III] is exemplified. can do.

R ¹ _n AlX _3-n ... [III] (In the formula [III], 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
~ 3. In the above general formula [III], 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, an n- Propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Such an organoaluminum compound (d)
Specifically, the following compounds are used. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

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

[0065] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ¹ ₃ Al,
_{^{R 1 n Al (OR 2)}} 3-n, represented by _{^{R 1 n Al (OAlR 4 2}} ) 3-n compounds are preferred, wherein R is isoalkyl group, compounds which are n = 2 is preferable.

In the present invention, when producing the ethylene / α-olefin copolymer [A], the above components (a), (b) and (c), and if necessary, component (d) The catalyst prepared by contacting is used. The order of contacting the components (a) to (d) at this time is arbitrarily selected, but preferably the components (c) and (b) are mixed and contacted, and then the component (a) is mixed and contacted, Further, if necessary, the component (d) is mixed and brought into contact.

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

The components (a), (b), (c) and
When mixing and contacting component (d) as necessary,
Minute (a) is usually 5 × 10^-6~ 5x
10 ^-FourMole, preferably 10^-Five~ 2 × 10^-FourIn moles
And the concentration of component (a) is about 10^-Four~ 2 × 10^-2
Mol / l, preferably 2 × 10^-Four-10^-2Mol /
In the liter range. Component (b) with aluminum
Atomic ratio with transition metal in minute (a) (Al / transition metal)
Is usually from 10 to 500, preferably from 20 to 200
You. Aluminum of component (d) optionally used
Atom (Al-d) and the aluminum atom (Al-
The atomic ratio (Al-d / Al-b) of b) is usually 0.02 to 3, and
More preferably, it is in the range of 0.05 to 1.5. Component (a), component
Minutes (b), component (c) and optionally component (d)
The mixing temperature at the time of mixing contact is usually -50 to 150 ° C,
Preferably it is -20 to 120 ° C., and the contact time is 1 minute to
50 hours, preferably 10 minutes to 25 hours.

The ethylene • α-
The catalyst used for the production of the olefin copolymer [A] is
5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atoms, preferably 10 × 10 ⁻⁴ gram atoms of transition metal atoms derived from component (a) per 1 g of component (c)
^{-5 to} 2 × 10 ^-4 gram atoms, and 10 ^{-3 to} 5 × 10 ^-2 gram atoms of aluminum atoms derived from components (b) and (d) per gram of component (c); Preferably, it is supported in an amount of 2 × 10 ^{−3 to} 2 × 10 ⁻² gram atoms.

Ethylene / α-olefin copolymer [A]
The catalyst used for the production of the component (a) as described above,
Component (b), component (c) and optionally component (d)
May be a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a olefin. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the components (a), (b), (c) and, if necessary, the component (d) as described above. Can be.

The olefin used in the prepolymerization includes 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
-Dodecene, 1-tetradecene and the like. Among them, ethylene used in the polymerization or a combination of ethylene and an α-olefin is particularly preferred.

In the prepolymerization, the above component (a) is
Usually 10 ^{-6 to} 2 × 10 ^-2 mol / l, preferably 5
× 10 ^-5 to 10 ^-2 used in an amount of mol / liter, the component (a) is the component (c) 1 g per usually 5 × 10 ^-6 ~5 × 1
It is used in an amount of 0 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. The atomic ratio (Al / transition metal) of aluminum of the component (b) to the transition metal in the component (a) is usually 10 to 5
00, preferably 20 to 200. The atomic ratio (Al-d) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) used as required.
/ Al-b) is usually from 0.02 to 3, preferably from 0.05 to 3.
It is in the range of 1.5. Prepolymerization temperature is -20 to 80 ° C,
Preferably it is 0 to 60 ° C., and the prepolymerization time is 0.1.
It is about 5 to 100 hours, preferably about 1 to 50 hours.

The prepolymerized catalyst is prepared, for example, as follows. That is, the carrier (component (c)) is suspended with an inert hydrocarbon. Next, an organic aluminum oxy compound (component (b)) is added to the suspension and reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. After adding a transition metal compound (component (a)) into the system and reacting for a predetermined time, the supernatant 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, whereby a prepolymerized catalyst can be obtained.

The olefin polymer produced by the prepolymerization is
0.1 to 500 g, preferably 0.2 g per 1 g of the carrier (c)
It is desirable that the amount be from 300 to 300 g, more preferably from 0.5 to 200 g. In addition, in the prepolymerized catalyst, the component (a) per gram of the carrier (c) is about 5 × as a transition metal atom.
10 ^{-6 to} 5 × 10 ^-4 gram atoms, preferably 10 ^-5 to 2
× 10 ⁻⁴ gram atoms, and the aluminum atom (Al) derived from the component (b) and the component (d) has a molar ratio (Al / M) to the transition metal atom (M) derived from the component (a). M), from 5 to 200, preferably from 10 to 150
Is desirably carried in an amount in the range described above.

The prepolymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Intrinsic viscosity [η] measured in decalin at least 135 ° C. in the coexistence of hydrogen in the range of 0.2 to 7 dl / g;
It is desirable to produce a prepolymer of preferably 0.5-5 dl / g.

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

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

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

In carrying out the slurry polymerization method or the gas phase polymerization method, the above-mentioned catalyst is usually used in a concentration of 10 ^-8 to 10 ^-3 gram atoms / transition metal atom in the polymerization reaction system.
It is desirable that it be used in an amount of 1 liter, preferably 10 ^-7 to 10 ^-4 gram atom / liter.

At the time of the main polymerization, the same organic aluminum oxy compound and / or organic aluminum compound (d) as the component (b) may be added. At this time, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the organic aluminum oxy compound and the organic aluminum compound and the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10 to 20
0, more preferably 15 to 150.

In the present invention, when performing the slurry polymerization method, the polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. The polymerization temperature is usually 0 to 120 ° C, preferably 20 ° C.
-100 ° C.

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

Further, the polymerization can be carried out in two or more stages under different reaction conditions. [Olefin-based elastomer [B]] The olefin-based elastomer [B] used in the present invention is a (co) polymer of ethylene or an α-olefin having 3 to 20 carbon atoms, and has a density of 0.900 g / cm ³ or less. , Preferably 0.8
In the range of 60 to 0.900 g / cm ³ ,
2.16kg melt flow rate (MF
R) is 0.01 to 100 g / 10 min, preferably 0.05
It is desirably in the range of ５０50 g / 10 minutes. Such an olefin-based elastomer [B] desirably has a crystallinity of less than 30% as measured by an X-ray diffraction method or is amorphous.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Can be mentioned. Among them, it is particularly preferable to use an α-olefin having 3 to 10 carbon atoms.

The olefin-based elastomer [B] used in the present invention is a component unit other than a component unit derived from an α-olefin, such as a component unit derived from a diene compound, as long as its properties are not impaired. May be included. For example, the component units permitted to be contained in the olefin elastomer [B] used in the present invention include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6- Methyl-1,5-heptadiene, 7-
Linear non-conjugated dienes such as methyl-1,6-octadiene;
Cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-
Isopropylidene-2-norbornene, 6-chloromethyl-5-
Cyclic non-conjugated dienes such as isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Component units derived from diene compounds can be mentioned.

These diene components can be used alone or in combination. The content of such a diene component is usually 10 mol% or less, preferably 0 to
5 mol%.

Specific examples of such an olefin-based elastomer [B] include a component unit derived from ethylene of 0 to 95 mol%, preferably 30 to 92 mol%.
Mol%, more preferably 50 to 90 mol%, having 3 to 3 carbon atoms.
Wherein the component units derived from 20 α-olefins are 1 to 1
00 mol%, preferably 4 to 70 mol%, more preferably 8 to 50 mol%, and the component unit derived from the diene component is 0 to 10 mol, preferably 0 to 5 mol%, more preferably 0 to 3 mol. % Of the copolymer.

The olefin elastomer [B] used in the present invention can be produced by a conventionally known method using a catalyst such as a Ti-based, V-based or Zr-based elastomer. [Ethylene-based copolymer composition] The ethylene-based copolymer composition of the present invention comprises the ethylene / α-olefin copolymer [A] and the olefin-based elastomer [B]. The weight ratio of the copolymer [A] to the olefin elastomer [B] ([A]:
[B]) is in the range of 99: 1 to 60:40, preferably 9
5: 5 to 70:30, more preferably 98: 2
It is desirable to be in the range of 80:20. In addition, the ethylene / α-olefin copolymer [A] and the olefin-based elastomer [B] have a ratio of the density of the olefin-based elastomer [B] to the density of the ethylene / α-olefin copolymer [A] ( [B] / [A]) are used in combination so as to be less than 1, preferably 0.905 to 0.980.

The ethylene copolymer composition of the present invention can be produced by using a known method, for example, by the following method. (1) A method of mechanically blending an ethylene / α-olefin copolymer [A], an olefin-based elastomer [B], and other components to be added as desired using an extruder, a kneader or the like.

(2) Ethylene / α-olefin copolymer [A], olefin-based elastomer [B], and other components to be added as required are mixed with a suitable good solvent (eg, hexane, heptane, decane, cyclohexane, A hydrocarbon solvent such as benzene, toluene and xylene) and then removing the solvent.

(3) After preparing a solution in which the ethylene / α-olefin copolymer [A], the olefin-based elastomer [B], and other components to be added as required are separately dissolved in a suitable good solvent. A method of mixing and then removing the solvent.

(4) A method in which the above methods (1) to (3) are combined. The ethylene-based copolymer composition of the present invention has a weather resistance stabilizer within a range that does not impair the purpose of the present invention.
Additives such as heat stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, etc It may be blended accordingly.

The ethylene copolymer composition of the present invention is processed into a film by ordinary air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding, or the like. Obtainable. The film formed in this manner has an excellent balance between transparency and rigidity, and has heat sealing properties, hot tack properties, heat resistance, and the like, which are characteristics of ordinary LLDPE. Further, since the composition distribution of the ethylene / α-olefin copolymer [A] is extremely narrow, there is no stickiness on the film surface. Further, since the stress is low even in a high shearing range, high-speed extrusion is possible, and power consumption is reduced, which is economically advantageous.

Films obtained by processing the ethylene-based copolymer composition of the present invention include standard bags, heavy bags, wrap films, raw paper, sugar bags, oily packaging bags, aqueous packaging bags, and foodstuffs. It is suitable for various packaging films for packaging, infusion bags, agricultural materials and the like. Further, it can be used as a multilayer film by being bonded to a substrate such as nylon or polyester. Further, it can also be used for blow infusion bags, blow bottles, extrusion molded tubes, pipes, tear-off caps, injection molded products such as daily necessities, fibers, and large molded products formed by rotational molding. Among them, it is particularly suitable for a wrap film.

[0095]

As described above, the ethylene copolymer composition of the present invention comprises:
Since a specific ethylene / α-olefin copolymer and a specific olefin-based elastomer are blended, a film having excellent moldability, excellent transparency and excellent mechanical strength can be produced.

[0096]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

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

[Film Impact] Measured by a pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisaku-sho, Ltd.

[0099]

[Production Example 1] Ethylene / α-olefin copolymer [A-
Production of 1] [Preparation of Catalyst Component] 7.9 kg of silica dried at 250 ° C. for 10 hours was suspended in 121 liters of toluene, and then cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 1.47 mol / L) 4
One liter was dropped in one hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 125 liters of toluene. 20 liters of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 28.4 mmol / l) was dropped into the system at 30 ° C. for 30 minutes, and further at 30 ° C. for 2 hours. Reacted. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 4.6 mg of zirconium per gram.

[Preparation of Preliminary Polymerization Catalyst] 4.3 kg of the solid catalyst obtained above was added to 160 liters of hexane containing 16 mol of triisobutylaluminum,
Preliminary polymerization of ethylene was performed at 5 ° C. for 3.5 hours to obtain a prepolymerized catalyst in which 3 g of ethylene polymer was prepolymerized per 1 g of the solid catalyst. [Η] of this ethylene polymer was 1.27 dl / g.

[Polymerization] Using a continuous fluidized-bed gas-phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. The prepolymerized catalyst prepared above was converted to 0.048 mmol in terms of zirconium atoms.
l / h, 10 mmol /
h, ethylene, 1-hexene, hydrogen, and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
083, hydrogen / ethylene = 0.0012, ethylene concentration = 23%).

The yield of the obtained ethylene / α-olefin copolymer (A-1) was 5.3 kg / h, the density was 0.927 g / cm ³ , and the MFR was 1.0 g / 10 min. And the number of unsaturated bonds is 0.0 per 1000 carbon atoms.
62, and 0.06 per polymer molecule;
The temperature at the maximum peak position of the endothermic curve measured by SC was 117.2 ° C., and the decane-soluble portion at 23 ° C. was 0.1%.
It was 22% by weight.

[0103]

Reference Example 1 [Film processing] Using the ethylene / α-olefin copolymer (A-1) produced in Production Example 1,
Using a single screw extruder of 0 mmφ · L / D = 26, a die of 25 mmφ, a lip width of 0.7 mm, a single slit air ring, air flow rate = 90 liter / min, extrusion rate = 9 g / min,
Under a condition of a blow ratio of 1.8, a take-up speed of 2.4 m / min, and a processing temperature of 200 ° C., a film having a thickness of 30 μm was blown.

The ethylene / α-olefin copolymer (A-
Table 3 shows the melt properties and film properties of 1).

[0105]

Example 1 [Preparation of composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and an olefin elastomer (B-1) shown in Table 2 (density: 0.88)
g / cm ³ ) with a weight ratio (A-1 / B-1) of 90/10, and tri (2,4-) as a secondary antioxidant with respect to 100 parts by weight of the resin. Di-t-butylphenyl)
0.05% by weight of phosphate, n as heat stabilizer
0.1% by weight of -octadecyl-3- (4'hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent.
Thereafter, using a conical tapered twin-screw extruder manufactured by Haake Corporation, the mixture was kneaded at a set temperature of 180 ° C. to obtain an ethylene copolymer composition.

[Film Processing] Using this ethylene copolymer composition, a 30 μm thick film was blown formed in the same manner as in Reference Example 1.

Table 3 shows the melt properties and film properties of the ethylene copolymer composition. Compared with Reference Example 1, an inflation film with improved film impact was obtained without impairing transparency and moldability (MT, FI).

[0108]

Example 2 [Preparation of composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and an olefin elastomer (B-2) shown in Table 2 (density: 0.1%) 8
7 g / cm ³ ) was used in the same manner as in Example 1 except that the weight ratio (A-1 / B-2) was 90/10 to obtain an ethylene copolymer composition.

[Film Processing] A film having a thickness of 30 μm was formed in the same manner as in Reference Example 1 using this ethylene-based copolymer composition.

Table 3 shows the melt properties and film properties of the ethylene copolymer composition. Compared with Reference Example 1, an inflation film with improved film impact was obtained without impairing transparency and moldability (MT, FI).

[0111]

Example 3 [Preparation of composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and an olefin elastomer (B-3) shown in Table 2 (density: 0.1%) 8
7 g / cm ³ ) was used in the same manner as in Example 1 except that the weight ratio (A-1 / B-3) was 90/10 to obtain an ethylene copolymer composition.

[Film Processing] A film having a thickness of 30 μm was formed in the same manner as in Reference Example 1 using this ethylene copolymer composition.

Table 3 shows the melt properties and film properties of the ethylene copolymer composition. Compared with Reference Example 1, an inflation film with improved film impact was obtained without impairing transparency and moldability (MT, FI).

[0114]

[Table 1]

[0115]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Pref. Mitsui Chemicals, Inc. 6-1-2 F-term in Mitsui Chemicals Co., Ltd. F-term (reference) 4J002 BB051 BB052 BB142 BB152 BB172 FD020 FD030 FD060 FD070 FD080 FD090 FD100 FD170 GA01 GC00 GF00 GG02 GT00 4J100 AA02P AA03Q AA04Q AA11AA DAA DAA DAA FA10

Claims (1)

[Claims] 1. [A] (Ai) ethylene and having 3 to 2 carbon atoms
(A-ii) having a density (d) of 0.880 to 0.960 g / cm ^3.
(A-iii) a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg within a range of 0.01 to 200 g / 10 minutes; and (A-iv) a differential scanning calorimeter (DSC). ), The temperature (Tm (° C.)) at the maximum peak position of the endothermic curve and the density (d) satisfy the relationship of Tm <400 × d−250, and (A−v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR) satisfy the relationship expressed by MT> 2.2 × MFR− ^0.84 , and (A-vi) the stress of the molten polymer at 190 ° C. is 2.4 ×
A flow index (FI (1 / sec)) defined by a shear rate when reaching 10 ⁶ dyne / cm ² and a melt flow rate (MFR) satisfy a relationship represented by FI> 75 × MFR; A-vii) When the decane-soluble part (W (% by weight)) and the density (d) at 23 ° C. are MFR ≦ 10 g / 10 min, W <80 × exp (−100 (d−0.88)) +0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
0.88)) + ethylene · α satisfying the relationship expressed by 0.1
60 to 99% by weight of an olefin copolymer, [B] (B-i) the density (d) is 0.990 g / cm ³ or less, and (B-ii) a melt flow rate at 190 ° C. under a load of 2.16 kg. 1 to 40% by weight of an olefin elastomer having a (MFR) in the range of 0.01 to 100 g / 10 minutes
Wherein the ratio ([B] / [A]) of the density of the [B] olefin-based elastomer to the density of the [A] ethylene / α-olefin copolymer is less than 1. Ethylene copolymer composition.