JP2002220500A - Ethylenic copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylenic copolymer composition enabling to produce a film having excellent thermal stability and formability with excellent balance of clarity and stiffness. SOLUTION: This ethylenic copolymer composition comprises a specified crystalline polyolefin and an ethylene-α-olefin copolymer having a density, a melt flow rate, a temperature at a maximum peak in the endothermic curve measured by DSC, a melt tension and a decane soluble fraction at 23 deg.C which are all controlled within each specified range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene copolymer composition, and more particularly, to a composition having better heat stability and moldability as compared with a conventionally known ethylene copolymer or an ethylene copolymer composition. The present invention relates to an ethylene copolymer composition capable of producing a film having excellent balance between transparency and rigidity.

[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.

Japanese Patent Application Laid-Open No. Sho 56-90810 discloses a method for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained using a Ziegler type catalyst, particularly a titanium catalyst. 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.

[0007] The present inventors have conducted intensive studies in view of such circumstances, and as a result, (a) a transition metal compound of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton; b) In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and C 3-20
Ethylene obtained by copolymerizing α-olefin of
The α-olefin copolymer was found to have excellent thermal stability and a narrow composition distribution. As a result of further research,
The ethylene-based copolymer composition obtained by blending the above-mentioned ethylene / α-olefin copolymer with a specific crystalline polyolefin is excellent in heat stability and fluidity (FI) in a high shear region, and is obtained. Film
The inventors have found that the balance between transparency and rigidity is excellent, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ethylene copolymer composition which is excellent in heat stability and moldability, and which can produce a film excellent in balance between transparency and rigidity. .

[0009]

SUMMARY OF THE INVENTION The ethylene copolymer composition according to the present invention is [A] (A-i) a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-i) ii) Density (d) is 0.88
0 to 0.960 g / cm ³ , and (A-iii) 19
The melt flow rate (MFR) at 0 ° C. and a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes, and (A-iv) the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC). (Tm (° C.)) and density (d) satisfy the relationship expressed by 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) the decane-soluble portion (W (% by weight)) and the density (d) at 23 ° C. satisfy MFR ≦ 1.
When 0 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 the ethylene / α-olefin copolymer satisfying the relationship of 0.1 and [B] the following groups (BI) to
(B-III) (BI) a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg is in a range of 0.01 to 100 g / 10 min, and a density is 0.950 g / cm ³ or more;
Ethylene homopolymer, or ethylene and C3-20
(B-II) having a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 100 g / 10 min, and a density of 0.990 g / cm ^3. A propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms (B-III) at 230 ° C. and a load of 2.16 kg A homopolymer of an α-olefin having 4 to 20 carbon atoms having a melt flow rate (MFR) in a range of 0.1 to 100 g / 10 min and a density of 0.990 g / cm ³ or more; 1 to 40% by weight of at least one crystalline polyolefin selected from copolymers of α-olefins
It is characterized by comprising.

[0010] Such an ethylene copolymer composition comprises:
A film excellent in heat stability and moldability and excellent in transparency and rigidity can be produced.

[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 a crystalline polyolefin [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

The ethylene / α-olefin copolymer [A] has the following properties (A-ii) to (A-vi). (A-ii) Density (d) is 0.880 to 0.960 g / cm
³ , preferably 0.990 to 0.935 g / cm ³ , more preferably 0.990 to 0.930 g / cm 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 was performed using a density gradient tube.

(A-iii) Melt flow rate (MFR)
Is 0.01 to 200 g / 10 min, preferably 0.05 to 200 g / 10 min.
50 g / 10 min, more preferably 0.1 to 10 g / 10
Desirably within the range of 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: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391.

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 ) The melt tension (MT (g)) and the melt flow rate (MFR) satisfy the relationship expressed by MT ≦ 2.2 × MFR− ^0.84 .

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 obtain a measurement sample,
Using Toyo Seiki Seisakusho's MT measuring instrument, resin temperature 190
° C, extrusion speed 15mm / min, winding speed 10-20
m / min, the nozzle diameter was 2.09 mmφ, and the nozzle length was 8 mm. At the time of pelletization, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant is added to the ethylene / α-olefin copolymer [A] in advance, which is stable against heat. 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.

(A-vi) The nFR-soluble component fraction (W (% by weight)) and the density (d) at room temperature are MFR ≦ 10
When g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1, preferably W <60 × exp (−100 (d−0.8)
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 When MFR> 10 g / 10 min, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
0.88)) + 0.1.

The amount of 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.

As described above, the relationship between the temperature (Tm) at the maximum peak position and the density (d) 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. It is desirable that:

Incidentally, the quantitative determination 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.

Further, the following formula

[0028]

(Equation 1)

[In the formula, PE indicates the mole fraction of the ethylene component in the copolymer, Po indicates the mole fraction of the α-olefin component, and PoE indicates the α-olefin / ethylene chain of all dyad chains. B value represented by the following formula: 1.00 ≦ B, preferably 1.01 ≦ B ≦ 1.50, more preferably 1.01 ≦ B ≦ 1.30. It is characterized by the following.

The B value is an index indicating the distribution state of each monomer component in the copolymer chain, and is represented by GJRay (Macromol
ecules, 10, 773 (1977) ), JCRandall (Macromolecules, 1
5 , 353, (1982)), J. Polymer Science, Polymer Physics E
d., 11 , 275 (1973)) and K. Kimura (Polymer, 25 , 441 (1984)) based on the reports of PE, Po and PoE as defined above.
Is calculated. The larger the B value, the smaller the number of block-like chains, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution.

The composition distribution B value was obtained 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, usually at a measurement temperature of 120 ° C. , Measurement frequency 25.0
5 MHz, spectrum width 1500 Hz, filter width 1
500 Hz, pulse repetition time 4.2 seconds, pulse width 7
The measurement was performed under measurement conditions of μ seconds and the number of integration times of 2,000 to 5,000 times, and PE, Po, and PoE were calculated from this spectrum.

The ethylene / α-olefin copolymer [A] constituting the ethylene-based copolymer composition of the present invention has the following (a) periodicity containing a ligand having a specific cyclopentadienyl skeleton. In the presence of a transition metal compound of Table IV, (b) an organoaluminum oxy compound, (c) a carrier and, if necessary, (d) an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and ethylene are used. ~ 2
And the density of the copolymer obtained with the α-olefin of 0.8 is 0.8.
It can be produced by copolymerizing to 80 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 transition metal compound represented by the following formula [I]. MLx ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the periodic table, L is a ligand coordinated to the transition metal atom M, and at least two Is a ligand L of
A cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or a C3-C3
A substituted cyclopentadienyl group having at least one group selected from 10 hydrocarbon groups, and the ligand L other than the (substituted) cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom,
X is the valence of the transition metal M. In the above formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, preferably zirconium.

L is a ligand which coordinates to the transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group,
An ethylcyclopentadienyl group or a carbon number of 3 to 10
Is a substituted cyclopentadienyl group having at least one substituent selected from the group consisting of the above-mentioned hydrocarbon groups, and the ligand L other than the (substituted) cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

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

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, such as decyl group Alkyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group and neophyl group.

Of these, alkyl groups are preferred, and n-propyl and n-butyl groups are particularly preferred. 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 by an alkyl group having 3 or more carbon atoms. A substituted cyclopentadienyl group is more preferred, and a 1,3-substituted cyclopentadienyl group is particularly preferred.

In the above formula [I], the ligand L other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom or a halogen atom. Atom, trialkylsilyl group or hydrogen atom.

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

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

Examples of the aryloxy group include a phenoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group. Such transition metal compounds represented by the general formula [I] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, (N-propylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n- Butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n
-Butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl)
Zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, 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,
Disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted, and tri-substituted include 1,2,3- and 1,2,4-substituted. 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], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1 -Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are 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 reacted with water, ice or water vapor 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 not more than 10%, preferably not more than 5%, particularly preferably not more than 2% 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 includes (a) a transition metal compound of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton, (b) an organoaluminumoxy compound, and (c) ) It is formed from a carrier, but if necessary, (d) an organoaluminum 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) R 1 n Al (}} OR 2) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R 1 n Al}} (OSiR 3 3) 3 _-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 Al}} (OAlR 4 2) a compound represented by _3-n, e.g., _{Et 2 AlOAlEt 2, (iso-} Bu) 2 AlOAl (iso-B
u) _{2, ^{etc.; (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 , _{^{etc.; (5) R 1 n Al}} (SiR 6 3) a compound represented by _3-n, e.g., (iso-Bu) ₂ AlSi Me _{3 ^{like; (6) R 1 n Al}} (n (R 7) AlR 8 2) a compound represented by _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , (iso-Bu) 2 AlN
(Et) Al (iso-Bu) ₂ etc.

[0063] 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, and 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.

In mixing and contacting the component (a), the component (b), the component (c) and, if necessary, the component (d), the component (a) is usually 5 × 10 ⁻⁶ per 1 g of the component (c). ~ 5x
It is used in an amount of 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, and the concentration of the component (a) is about 10 ^-4 to 2 × 10 ^-2.
Mol / liter, preferably 2 × 10 ^-4 to 10 ^-2 mol /
In the liter range. Atomic ratio of aluminum of component (b) to transition metal in component (a) (Al / transition metal)
Is usually from 10 to 500, preferably from 20 to 200. The aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-
The atomic ratio (Al-d / Al-b) of b) is usually in the range of 0.02 to 3, preferably 0.05 to 1.5. The mixing temperature at the time of mixing and contacting the component (a), the component (b), the component (c) and, if necessary, the component (d) 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-α obtained as described above
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~ 2 × 10^-2Mol / l, preferably 5
× 10^-Five-10^-2Used in the amount of moles / liter, the ingredients
(A) is usually 5 × 10 per 1 g of component (c).^-6~ 5 × 1
0^-FourMole, preferably 10 ^-Five~ 2 × 10^-FourUse in mole amount
Can be. Aluminum of component (b) and component (a)
The atomic ratio with the transition metal (Al / transition metal) is usually 10 to
500, preferably 20-200. If necessary
The aluminum atom (Al-d) of the component (d) used
The atomic ratio (Al) of the aluminum atom (Al-b) of the component (b)
-d / Al-b) is usually 0.02 to 3, preferably 0.05.
~ 1.5. Prepolymerization temperature is -20 to 80
° C, preferably 0 to 60 ° C, and the prepolymerization time is
0.5 to 100 hours, preferably about 1 to 50 hours
You.

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 an α-olefin is carried out in a gas phase or in a slurry liquid phase. 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.

When the slurry polymerization method or the gas phase polymerization method is used, 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 the slurry polymerization method is carried out, 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 having different reaction conditions. [Crystalline Polyolefin [B]] In the present invention, at least one kind of crystalline polyolefin selected from the following (BI) to (B-III) is used as the crystalline polyolefin [B].

"Crystalline Polyolefin (BI)" The crystalline polyolefin (BI) used in the present invention is an ethylene homopolymer having a crystallinity of 65% or more as measured by an X-ray diffraction method, or an ethylene homopolymer. A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms having a crystallinity of 65% or more and a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg of 0.01 to 100 g / 10. Min, preferably in the range of 0.05 to 50 g / 10 min and a density of 0.950 g / cm ³ or more, preferably 0.950 to 0.9 g / cm ³ .
It is preferably in the range of 970 g / cm ³ .

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.

In such a copolymer, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but generally ranges from 100/0 to 99/1. Preferably 100 / 0-9
It is 9.5 / 0.5.

The crystalline polyolefin (B-I) used in the present invention may be 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. And other component units.

The component units other than the component unit derived from α-olefin include, for example, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl- Linear non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5- Methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl
Cyclic non-conjugated dienes such as 2-norbornene; diene compounds such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene And component units derived from

The diene components can be used alone or in combination. Also, the content of the diene component is
Usually, it is 0 to 1 mol%, preferably 0 to 0.5 mol%. Such a crystalline polyolefin (B-I) can be produced by a conventionally known method. "Crystalline polyolefin (B-II)" The crystalline polyolefin (B-II) used in the present invention is a propylene homopolymer having a crystallinity of 50% or more as measured by an X-ray diffraction method, or propylene and ethylene. And carbon number of 4 to 2
A copolymer with at least one olefin selected from α-olefins having a crystallinity of 30% or more and a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg. ) Is 0.1 to 100 g /
10 minutes, preferably in the range of 0.5 to 50 g / 10 minutes, and the density is 0.990 g / cm ³ or more, preferably 0.9.
It is preferably in the range of 00 to 0.920 g / cm ³ .

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Can be. Among them, carbon number 4-1
It is particularly preferred to use an α-olefin of 0.

Propylene, ethylene and carbon number 4 to
In a copolymer with at least one selected from α-olefins having 20 carbon atoms, propylene, ethylene and carbon atoms of 4
The molar ratio of propylene to α-olefin (propylene / α-olefin (including ethylene)) varies depending on the type of α-olefin, but generally ranges from 100/0 to 90/1.
0, preferably 100/0 to 95/5.

The crystalline polyolefin (B-II) used in the present invention is derived from the diene compound used in the above-mentioned crystalline polyolefin (B-I) as long as its properties are not impaired. It may contain a component unit or the like. The content of the diene component is usually 0 to 1 mol%, preferably 0 to 0.5 mol%.

Such a crystalline polyolefin (B-II)
Can be produced by a conventionally known method. "Crystalline polyolefin (B-III)" The crystalline polyolefin (B-III) used in the present invention has a crystallinity of 30% or more measured by an X-ray diffraction method and has 4 to 2 carbon atoms.
0 is a homopolymer of α-olefin or a copolymer of α-olefin of 4 to 20 carbon atoms having the same degree of crystallinity of 30% or more, and has a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg. ) Is 0.1 to 100 g / 10
Min, preferably in the range of 0.5 to 50 g / 10 min,
Density 0.900 g / cm ³ or more, preferably 0.900
It is preferably in the range of 0.920 g / cm ³ .

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

At least two kinds of α having 4 to 20 carbon atoms
Α-olefin (a) selected from α-olefins having 4 to 20 carbon atoms in the copolymer comprising α-olefin
And the molar ratio of (a) / (b) to another α-olefin (b) selected from α-olefins having 4 to 20 carbon atoms
Varies depending on the type of α-olefin, but is generally 100/0 to 90/10, preferably 100/0 to 95
/ 5.

The crystalline polyolefin (B-III) used in the present invention is in a range that does not impair its properties.
It may contain a component unit derived from the diene compound used for the crystalline polyolefin (BI) as described above. The content of the diene component is usually 0 to 1 mol%,
Preferably it is 0-0.5 mol%.

Such a crystalline polyolefin (B-II
I) can be produced by a conventionally known method. [Ethylene-based copolymer composition] The ethylene-based copolymer composition of the present invention comprises the ethylene / α-olefin copolymer [A] and the crystalline polyolefin [B]. The weight ratio ([A]: [B]) of the copolymer [A] to the crystalline polyolefin [B] is 9
9: 1 to 60:40, preferably 98: 2 to 70: 3
0, more preferably in the range of 95: 5 to 80:20.

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], a crystalline polyolefin [B], and other optional components with an extruder, a kneader or the like.

(2) An ethylene / α-olefin copolymer [A], a crystalline polyolefin [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 crystalline polyolefin [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, and antioxidants are required. It may be blended accordingly.

The ethylene copolymer composition of the present invention can be 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.

Films obtained by processing the ethylene 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, tubes, pipes, tear-off caps by extrusion molding, injection molded articles such as daily necessities, fibers, and large molded articles by rotational molding. Of these, it is particularly suitable for infusion bags.

[0102]

As described above, the ethylene copolymer composition of the present invention comprises:
Since a specific ethylene / α-olefin copolymer and a specific crystalline polyolefin are blended, a film having excellent heat stability and moldability, and excellent balance between transparency and rigidity can be produced.

[0103]

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. [Flow index (FI)] 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 obtained by extruding the resin from the capillary while changing the shear rate.
It is determined by measuring the stress at that time. That is, using the same sample as in the MT measurement, and manufactured by Toyo Seiki Seisakusho,
Using a capillary flow property tester, the resin temperature is measured at 190 ° C., and the shear stress is measured in a range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / 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 [Haze (cloudiness)] ASTM-D It was measured according to -1003-61.

[Tensile test] Using a dumbbell (JIS No. 1), a test piece was punched out in the machine direction (MD) and the transverse direction (TD) with respect to the film forming direction, and the distance between the chucks was 86 m.
m, tensile modulus (YM) and elongation at break (EL) were measured at a crosshead speed of 200 mm / min.

[0107]

[Production Example 1] Ethylene / α-olefin copolymer [A-
Production of 1] [Preparation of Catalyst Component] 6.3 kg of silica dried at 250 ° C. for 10 hours was suspended in 100 liters of toluene, and then cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 0.96 mol / L)
41 liters were added dropwise over 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 60 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 washed with toluene 125
Resuspended in liters. To this system, 15 liters of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr = 42.7 mmol / l) was added dropwise at 30 ° C. over 30 minutes.
Allowed to react for hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 6.2 mg of zirconium per gram.

[Preparation of Preliminary Polymerization Catalyst] To 300 liters of hexane containing 14 mol of triisobutylaluminum, 8.5 kg of the solid catalyst obtained above was added.
By pre-polymerizing ethylene at 35 ° C. for 7 hours,
A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[Polymerization] Ethylene and 1-hexene were copolymerized at a total pressure of 18 kg / cm ² -G and a polymerization temperature of 80 ° C. using a continuous fluidized bed gas phase polymerization apparatus. The prepolymerized catalyst prepared in the above [Preparation of prepolymerized catalyst] is continuously supplied at a rate of 0.15 mmol / h in terms of zirconium atom and triisobutylaluminum at a rate of 10 mmol / h to maintain a constant gas composition during the polymerization. , 1-hexene, hydrogen and nitrogen were supplied continuously (gas composition: 1-hexene / ethylene = 0.020, hydrogen / ethylene = 6.6)
× 10 ^-4 , ethylene concentration = 16%).

The yield of the obtained ethylene / α-olefin copolymer (A-1) was 5.0 kg / hr, the density was 0.923 g / cm ³ , and the melt flow rate (M
FR) is 1.1 g / 10 min, the maximum peak of the melting point in DSC is 116.8 ° C., the melt tension (MT) is 1.5 g, and the decane-soluble portion at 23 ° C. is 0.02% by weight. And the number of unsaturated bonds is 1
0.09 per 000 and 0.1 per molecule of polymer
The B value indicating the distribution of α-olefins in the copolymer chain was 1.02.

[0111]

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

Table 3 shows the melt properties and film properties of the ethylene copolymer composition.

[0113]

Example 1 [Preparation of Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-1) shown in Table 2 were mixed at a mixing ratio (A -1 / B-
1) Dry blend at 90/10, and further add tri (2,4-di-t-t-) as a secondary antioxidant to 100 parts by weight of resin.
Butylphenyl) phosphate at 0.05 parts by weight, and n-octadecyl-3- (4'-hydroxy-
0.1 parts by weight of 3 ', 5'-di-t-butylphenyl) propionate and 0.05 parts by weight of calcium stearate as a hydrochloric acid absorbent were blended. 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] 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.

As compared with Reference Example 1, the fluidity (FI) in the high shear region was improved, and the transparency and rigidity of the obtained film were improved.

[0116]

Example 2 [Preparation of Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-2) shown in Table 2 were mixed at a mixing ratio (A -1 / B-
2) An ethylene copolymer composition was obtained in the same manner as in Example 1 except for using 90/10.

[Film Processing] Using this ethylene copolymer composition, a 30 μm thick film was formed in the same manner as in Production Example 1. Table 3 shows the melt properties and film properties of the ethylene copolymer composition.

Compared with Reference Example 1, the fluidity (FI) in the high shear region was improved, and the rigidity of the obtained film was improved.

[0119]

Example 3 [Preparation of Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-3) shown in Table 2 were mixed at a mixing ratio (A -1 / B-
3) An ethylene-based copolymer composition was obtained in the same manner as in Example 1 except that 90/10 was used.

[Film Processing] A film having a thickness of 30 μm was formed in the same manner as in Production 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, the fluidity (FI) in the high shear region was improved, and the rigidity of the obtained film was improved.

[0122]

Example 4 [Preparation of Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the crystalline polyolefin (B-4) shown in Table 2 were mixed at a mixing ratio (A -1 / B-
4) An ethylene copolymer composition was obtained in the same manner as in Example 1 except for using 90/10.

[Film Processing] A film having a thickness of 30 μm was formed in the same manner as in Production Example 1 by using this ethylene copolymer composition. Table 3 shows the melt properties and film properties of the ethylene copolymer composition.

Compared with Reference Example 1, the fluidity (FI) in the high shear region was improved, and the rigidity of the obtained film was improved.

[0125]

Example 5 [Preparation of composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 was mixed with a crystalline polyolefin (B-5) shown in Table 2 (A-5). -1 / B-
5) An ethylene copolymer composition was obtained in the same manner as in Example 1 except that 90/10 was used.

[Film Processing] A 30 μm-thick film was formed from this ethylene copolymer composition in the same manner as in Production Example 1. Table 3 shows the melt properties and film properties of the ethylene copolymer composition.

Compared with Reference Example 1, the fluidity (FI) in the high shear region was improved, and the rigidity of the obtained film was improved.

[0128]

[Table 1]

[0129]

[Table 2]

[0130]

[Table 3]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiichi Ikeyama 580-32 Nagaura, Sodegaura City, Chiba Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Toshiyuki Tsutsui 6-1 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture -2 F-term (reference) in Mitsui Chemicals, Inc. DA12 DA14 DA22 DA28 DA39 DA42 DA43 FA09 FA10 FA19 FA22 JA28 JA51 JA58 JA59 JA64

Claims (1)

[Claims] (A) A copolymer of (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-ii) a density (d) of 0.880 to 0.8. 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 represented by 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) a decane-soluble portion at 23 ° C. (W (% by weight))
When 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)) + 0.1% by weight of an ethylene / α-olefin copolymer satisfying the relationship expressed by 0.1: [B] The following groups (BI) to (B-III) A) 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 min and a density of 0.950 g / cm ³ or more;
Ethylene homopolymer, or ethylene and C3-20
(B-II) having a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg within a range of 0.1 to 100 g / 10 min, and a density of 0.990 g / cm ^3. A propylene homopolymer or a copolymer of propylene and at least one olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms (B-III) at 230 ° C. under a load of 2.16 kg A homopolymer of an α-olefin having 4 to 20 carbon atoms having a melt flow rate (MFR) in a range of 0.1 to 100 g / 10 min and a density of 0.990 g / cm ³ or more; 1 to 40% by weight of at least one crystalline polyolefin selected from copolymers of α-olefins
An ethylene copolymer composition comprising: