JPH0665443A - Ethylenic copolymer composition - Google Patents

Abstract

PURPOSE:To obtain an etylenic copolymer composition, composed of a specific ethylene.alpha-olcopolymer and a specified PE in a specific proportion, excellent in moldability, transparency, mechanical strength and blocking resistance and useful as films, etc. CONSTITUTION:The objective composition is composed of (A) a copolymer of ethylene and a 3-20C alpha-olefin having 0.880-0.960g/cm<3> density, 0.01-200g/10min melt flow rate(MFR), the maximum peak T ( deg.C) measured by the differential scanning calorimetry(DSC) and a density (d) satisfying the relationship of T<400X(d)-250 and a melt tension(MT) and a melt flow rate (MFR) satisfying the relationship of MT<=2.2XMFR<-0.84> and (B) a low-density PE having the melt flow rate within the range of 0.1-50g/10min and prepared by a high-pressure radical method. The weight ratio of the components (A) to (B) is within the range of (99/1) to (60/40).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an ethylene-based copolymer composition, and more specifically, it has improved transparency and mechanical strength as compared with conventionally known ethylene-based copolymers or ethylene-based copolymer compositions. The present invention relates to a novel ethylene copolymer composition capable of producing an excellent film and having excellent moldability.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when molding blown film at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform high-speed molding stably, an ethylene copolymer with a large melt tension relative to its molecular weight should be selected. Must. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer is small under high shear during extrusion from the economical aspect such as quality improvement of the molded product and reduction of power consumption during molding.

By the way, low-density polyethylene produced by the high-pressure radical method has a large melt tension as compared with an ethylene-based copolymer produced by using a Ziegler type catalyst, and is therefore used for applications such as films and hollow containers. However, the high-pressure radical method low-density polyethylene is inferior in mechanical strength such as tensile strength, tear strength or impact strength, and is also inferior in heat resistance and stress crack resistance.

On the other hand, a method for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in JP-A-56-90810. Publication or JP-A-6
No. 0-106806 is proposed.

However, in general, an ethylene-based polymer obtained by using a titanium-based catalyst, particularly a low-density ethylene-based copolymer has a wide composition distribution and has a problem that a molded product such as a film is sticky.

[0006] Among ethylene-based polymers produced by using a Ziegler type catalyst, an ethylene-based polymer obtained by using a chromium-based catalyst is relatively excellent in melt tension but poor in thermal stability. There are disadvantages. It is considered that this is because the chain end of the ethylene polymer produced using the chromium catalyst is likely to be an unsaturated bond.

Among the Ziegler-type catalyst systems, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded article such as a film is 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. However, like the ethylene-based polymer obtained using the above chromium-based catalyst, it is expected that the thermal stability is poor. Further, since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Therefore, if an ethylene-based polymer having an excellent melt tension, a small stress in the high shear region, a good thermal stability, an excellent mechanical strength, and a narrow composition distribution appears, its industrial use will be improved. The target value is extremely large.

The inventors of the present invention use (a) a transition metal compound of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton and (b) an organoaluminumoxy compound for olefin polymerization. It has been found that an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst has excellent thermal stability and a narrow composition distribution. As a result of further research, an ethylene-based copolymer composition obtained by blending this ethylene / α-olefin copolymer with a specific low-density polyethylene obtained by a high-pressure radical polymerization method It was found that the film obtained was excellent in transparency and the obtained film was excellent in transparency and mechanical strength, and thus completed the present invention.

[0010]

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

[0011]

SUMMARY OF THE INVENTION An ethylene-based copolymer composition according to the present invention is a copolymer of [A] ethylene and an α-olefin having 3 to 20 carbon atoms, and (i) has a density (d) of 0.880-
The range is 0.960 g / cm ³ , (ii) 190 ° C.,
Melt flow rate under 2.16 kg load (MF
R) is in the range of 0.01 to 200 g / 10 minutes, and (ii)
i) The maximum peak of melting point in DSC (T (° C.)) and the density (d) satisfy the relationship of T <400 × d-250, and (iv) melt tension at 190 ° C. (MT (g)). And melt flow rate (M
FR) satisfies the relationship represented by MT ≦ 2.2 × MFR ^−0.84 (2), and (v) the decane-soluble part (W (% by weight)) and the density (d) at 23 ° C. MFR ≦ 1
At 0 g / 10 minutes, W <80 * exp (-100 (d-0.88)) + 0.1 MFR> At 10 g / 10 minutes, W <80 * (MFR-9) ^0.26 * exp (-100 (D-
0.88)) + 0.1, an ethylene / α-olefin copolymer satisfying the relationship, and [B] a low-density polyethylene prepared by a high-pressure radical method, wherein (i) the melt flow rate (MFR) is 0.9. 1-5
Within the range of 0 g / 10 minutes, (ii) the molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MF) measured by GPC.
R) is 7.5 × log (MFR) -1.2 ≦ Mw / Mn ≦ 7.5 × log
(MFR) +12.5 consisting of a high-pressure radical method low-density polyethylene satisfying the relationship, and the weight ratio of the ethylene / α-olefin copolymer [A] and the high-pressure radical method low-density polyethylene [B] ( [A]: [B]) is 99: 1 to 6
It is characterized by being in the range of 0:40.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The ethylene copolymer composition according to the present invention will be described in detail below. The ethylene-based copolymer composition according to the present invention comprises an ethylene / α-olefin copolymer [A] and a high pressure radical method low density polyethylene [B].

[Ethylene / α-olefin copolymer [A]] The ethylene / α-olefin copolymer [A] constituting the ethylene copolymer composition according to the present invention comprises ethylene and 3 to 20 carbon atoms. 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, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

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

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 at the measurement temperature. 120
℃, measurement frequency 25.05MHz, spectrum width 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of.

The ethylene / α-olefin copolymer [A] used in the present invention has the following characteristics (i) to (v). (I) The density (d) is 0.880 to 0.960 g / cm ^3.
However, it is preferably 0.890 to 0.935 g /
cm ³ , more preferably 0.905 to 0.930 g / cm ^3.
It is desirable to be in the range of.

The density (d) is 2.90 at 190.degree.
The strand obtained at the time of measuring the melt flow rate (MFR) under a load of 16 kg was heat treated at 120 ° C. for 1 hour, and
After slowly cooling to room temperature over a period of time, measurement was performed using a density gradient tube.

(Ii) The melt flow rate (MFR) is
It is in the range of 0.01 to 200 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 1
It is preferably in the range of 0 g / min.

The melt flow rate (MFR) is
Measured according to ASTM D1238-65T under conditions of 190 ° C. and 2.16 kg load. (Iii) The temperature (T (° C.)) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) and the density (d) satisfy the relationship represented by T <400 × d−250. However, it is preferable that the relationship represented by T <450 × d-297 is more preferable, T <500 × d-344 is more preferable, and T <550 × d-391 is particularly preferable.

The temperature (T (° C.)) at the maximum peak position in the endothermic curve was obtained by packing about 5 mg of a sample in an aluminum pan, raising the temperature to 200 ° C. at 10 ° C./minute, and holding at 200 ° C. for 5 minutes. ℃ / min to room temperature, then 10 ℃
It is determined from the endothermic curve when the temperature is raised in 1 / min. The measurement is
A Perkin Elmer DSC-7 type device was used.

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

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

(V) The n-decane-soluble component amount fraction (W (wt%)) and the density (d) at 23 ° C. are MFR ≦ 10.
When g / min, W <80 × exp (−100 (d−0.88)) + 0.1, preferably W <60 × exp (−100 (d−0.8)
8)) + 0.1, more preferably W <40 × exp (−100 (d−0.8)
8)) +0.1 When MFR> 10 g / min, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

The amount of the n-decane-soluble component of the ethylene / α-olefin copolymer (the smaller the soluble component, the narrower the composition distribution) was measured by measuring about 3 g of the copolymer with n-decane 45.
In addition to 0 ml, the solution is dissolved at 145 ° C., cooled to 23 ° C., the n-decane-insoluble part is removed by filtration, and the n-decane-soluble part is recovered from the filtrate.

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

Further, in the ethylene / α-olefin copolymer [A], the number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms, and 1 per polymer molecule. The following is desirable.

The quantification of unsaturated bonds was carried out by ¹³ C-NMR.
Is used to identify signals other than double bonds, ie, 10
The area intensity of the signal in the range of ˜50 ppm and the signal attributed to the double bond, that is, the signal in the range of 105 to 150 ppm is determined from the integral curve and determined from the ratio.

Further, the following formula

[0029]

[Equation 1]

[Wherein PE represents the mole fraction of the ethylene component contained in the copolymer, Po represents the mole fraction of the α-olefin component, and PoE represents the α-olefin / ethylene chain of the entire dyad chain. The B value represented by the formula] is 1.00 ≦ B, preferably 1.01 ≦ B ≦ 1.50, and more preferably 1.01 ≦ B ≦ 1.30. It is characterized by

The above B value is an index showing the distribution state of each monomer component in the copolymer chain, and is GJRay (Macromol
ecules, 10 , 773 (1977)), JC, Randall (Macromolecules, 1
5 , 353, (1982)), J. Polymer Science, Polymer Physics E
d., 11 , 275 (1973)), and K. Kimura (Polymer, 25,441 (1984)) and others, based on the report, PE, Po and PoE defined above.
It is calculated by obtaining 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 determined by measuring the ¹³ C-NMR spectrum of a sample in which about 200 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at a measurement temperature of usually 120 ° C. , Measurement frequency 25.
By measuring PE, Po, and PoE from this spectrum, measurement was performed under the measurement conditions of 05 MHz, spectrum width 1500 Hz, filter width 1500 Hz, pulse repetition time 4.2 seconds, pulse width 7 μsec, and number of integration times 2000 to 5000 times. It was calculated.

Ethylene / α-having the above characteristics
The olefin copolymer [A] is obtained by adding (a) a transition metal compound and (b) an organoaluminum oxy compound described below in the presence of an olefin polymerization catalyst to ethylene and α-C 3-20. It can be produced by copolymerizing an olefin with the resulting copolymer so that the density of the obtained copolymer is 0.880 to 0.960 g / cm ^3, and (a) a transition metal compound as described below, In the presence of (b) an organoaluminum oxy compound, (c) a carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and 3 to 2 carbon atoms are present.
And the density of the copolymer obtained is 0.
It can be produced by copolymerization so that the amount becomes 880 to 0.960 g / cm ³ .

The (a) transition metal compound (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 of them are included. The ligand L of
Cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, or C3-C3
10 is a substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups, and the ligand L other than the (substituted) cyclopentadienyl group has 1 to 12 carbon atoms.
Is a hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or 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 coordinated to the transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one kind of substituent selected from the hydrocarbon groups, and the ligand L other than the (substituted) cyclopentadienyl group has 1 to 12 carbon atoms.
Is a hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. The substituted cyclopentadienyl group has at least 1 when it has two or more substituents.
The number of the substituents may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents may be a methyl group, an ethyl group or a carbon number 3
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, decyl group, etc. Examples thereof include an alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neofil group.

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

In the above 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 or 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, an aryl group and an aralkyl group, and more specifically, a methyl group, an ethyl group and 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, alkyl group such as decyl group; cyclopentyl group, cyclohexyl group, etc. A cycloalkyl group of phenyl group,
Examples thereof include aryl groups such as tolyl group; and aralkyl groups such as benzyl group and neophyll group.

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

Examples of the aryloxy group include a phenoxy group and the like. Examples of the halogen atom include 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 bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis. (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 methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, 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,
The disubstituted forms of the cyclopentadienyl ring include 1,2- and 1,3-substituted products, and the trisubstituted products include 1,2,3- and 1,2,4-substituted products. In the present invention, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Among these transition metal compounds represented by the general formula [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 (b) organoaluminum oxy compound 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, and can be used in JP-A-2- 2768
It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent Application Laid-Open No. 07-2007.

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

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it 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 organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride;
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Of these, trialkylaluminums and trialkylaluminums 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 Isoprenylaluminum can also be used.

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

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

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

The carrier (c) used in the present invention (hereinafter sometimes referred to as "component (c)") is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to. A 200 μm granular or particulate solid is used. Among these, porous oxides are 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 etc. or mixtures thereof, eg 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
Etc. can be illustrated. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

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

The carrier (c) has different properties depending on its type 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. , The pore volume is 0.3-
It is preferably 2.5 cm ² / g. The carrier is, if necessary, 100 to 1000 ° C, preferably 150 to 70 ° C.
It is used after firing at 0 ° C.

Further, the carrier (c) which can be used in the present invention includes a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 2 carbon atoms.
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers, and polymers or copolymers containing vinylcyclohexane or styrene as a main component.

The catalyst used in the present invention includes the above-mentioned (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) formed from a carrier,
You may use the (d) organoaluminum compound as needed.

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

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

Such an organoaluminum compound (d)
Specifically, the following compounds are used. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri-2-ethylhexyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (d), a compound represented by the following general formula [III] can be used. R ¹ _n AlY _3-n ... [III] (In the formula [III], R ¹ is the same as above, and Y is —OR ²
Group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used.

(1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (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) A compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like; (4) compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2
(5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ;

[0065]

[Chemical 1]

Among the organoaluminum compounds represented by the above general formulas [II] and [III], the general formula R ¹ ₃ Al,
The compounds represented by R ¹ _n Al (OR ² ) _3-n and R ¹ _n Al (OA1R ⁴ ₂ ) _3-n are preferable, and the compound in which R is an isoalkyl group and n = 2 is particularly preferable.

In the present invention, when the ethylene / α-olefin copolymer [A] is produced, the above-mentioned component (a), component (b) and component (c) and, if necessary, component (d). A catalyst prepared by contacting with is used. The contacting order of the components (a) to (d) at this time is arbitrarily selected, but preferably the component (c) and the component (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-mentioned components (a) to (d) can be carried out in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride , Halogenated hydrocarbons such as chlorobenzene and dichloromethane, or a mixture thereof.

Component (a), component (b), component (c) and
And, if necessary, mixing and contacting the component (d),
Minute (a) is usually 5 × 10 per 1 g of component (c).^-6~ 5x
10 ^-FourMol, preferably 10^-Five~ 2 x 10^-FourIn molar amounts
The concentration of component (a) used is about 10^-Four~ 2 x 10^-2
Mol / liter, preferably 2 × 10^-Four-10^-2Mol /
It is in the liter range. Component (b) made of aluminum
Atomic ratio with transition metal in minute (a) (Al / transition metal)
Is usually 10 to 500, preferably 20 to 200
It Aluminum as the component (d) used as necessary
Atom (Al-d) and the aluminum atom of the component (b) (Al-
The atomic ratio (Al-d / Al-b) of b) is usually 0.02 to 3, preferably.
It is preferably in the range of 0.05 to 1.5. Ingredient (a)
Minute (b), component (c) and optionally component (d)
The mixing temperature at the time of mixing and contacting is usually -50 to 150 ° C,
The temperature is preferably −20 to 120 ° C., and the contact time is 1 minute to
It is 50 hours, preferably 10 minutes to 25 hours.

Ethylene.α-obtained as described above
The olefin copolymer [A] polymerization catalyst comprises the component (c) 1
The transition metal atom derived from the component (a) is 5 × 10 ⁻⁶ per g.
~ 5 x 10 ^-4 gram atom, preferably 10 ^-5 to 2 x 10
^-4 g-atom, and 10 ^{-3 to} 5 x 10 ^-2 g-atom, preferably 2 x 1 aluminum atom derived from component (b) and component (d) per gram of component (c).
It is preferably loaded in an amount of 0 ^{−3 to} 2 × 10 ⁻² gram atom.

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)
It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above component (a), component (b), component (c) and, if necessary, component (d). You can

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

In the prepolymerization, the above component (a) is
Usually 10 ^{−6 to} 2 × 10 ⁻² mol / liter, preferably 5
It is used in an amount of × 10 ⁻⁵ to 10 ⁻² mol / liter, and the component (b) is usually 5 × 10 ^{−6 to} 5 × 1 per 1 g of the component (c).
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) and 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) that are used as necessary.
/ Al-b) is usually 0.02 to 3, preferably 0.05 to
It is in the range of 1.5. The prepolymerization temperature is -20 to 80 ° C,
The temperature is preferably 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 prepolymerization catalyst is prepared, for example, as follows. That is, the carrier (component (c)) is suspended in inert hydrocarbon. Next, an organoaluminum oxy compound (component (b)) is added to this suspension and reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon. A transition metal compound (component (a)) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduced therein to produce a preliminary polymerization catalyst by preliminary polymerization. The olefin polymer is 1 g of the carrier (c).
It is desirable that the amount is 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g. In addition, in the prepolymerization catalyst, the component (a) is present as a transition metal atom in an amount of about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ per 1 g of the carrier (c).
The aluminum atom (Al) derived from component (b) and component (d) is supported by an amount of gram atom, preferably from 10 ^{-5 to} 2 × 10 ^-4 gram atom, and is a transition metal derived from component (a). The molar ratio (Al / M) to the atom (M) is 5
It is desirable that the carrier be supported in an amount of ˜200, preferably 10 to 150.

The prepolymerization can be carried out 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 of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

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

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

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

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

In the main polymerization, the same organoaluminumoxy compound and / or organoaluminum 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 organoaluminum oxy compound and the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10-20
The range is 0, more preferably 15 to 150.

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

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

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. [High Pressure Radical Method Low Density Polyethylene [B]] Next, the high pressure radical method low density polyethylene [B] used in the present invention will be specifically described.

High pressure radical method low density polyethylene [B]
Is a highly branched polyethylene having long chain branches produced by so-called high pressure radical polymerization, and
According to D1238-65T, the MFR measured under the condition of 190 ° C. and 2.16 kg load is in the range of 0.1 to 50 g / 10 minutes, but preferably in the range of 0.2 to 10 g / 10 minutes. , 0.2 to 8 g / 10 minutes is more preferable.

The high-pressure radical method low-density polyethylene according to the present invention has a molecular weight distribution index (Mw) measured by gel permeation chromatography (GPC).
/ Mn; where Mw: weight average molecular weight, Mn: number average molecular weight) and melt flow rate (MFR) are 7.5 × log (MFR) -1.2 ≦ Mw / Mn ≦ 7.5 × log
(MFR) +12.5 preferably 7.5 × log (MFR) −0.5 ≦ Mw / Mn ≦ 7.5 × log
(MFR) +12.0, more preferably 7.5 × log (MFR) ≦ Mw / Mn ≦ 7.5 × log (MFR)
It satisfies the relationship indicated by +12.0.

The molecular weight distribution (Mw / Mn) of the high-pressure low-density polyethylene was measured as follows using GPC-150C manufactured by Millipore. Separation column is TS
K GNH HT, column size is 72m diameter
m, length 600 mm, column temperature 140 ° C., mobile phase using o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (Takeda Yakuhin) 0.025 wt% as an antioxidant, 1.0 ml The sample concentration is 0.
The sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <1000 and Mw> 4 × 10 ^6.
Is manufactured by Tosoh Corporation, and 1000 <Mw <4 × 1
As for 0 ⁶ , a product manufactured by Pressure Chemical Co. was used.

The high pressure radical method low density polyethylene according to the present invention has a density (d) of 0.910 to 0.930 g.
It is preferably in the range of / cm ³ . Density is 190
Strands obtained during melt flow rate (MFR) measurement at 2.16 kg load at 120 ° C
After heat treatment for 1 hour and cooling to room temperature over 1 hour, measurement is performed with a density gradient tube.

The high-pressure radical method low-density polyethylene [B] according to the present invention has a swell ratio indicating the degree of long-chain branching, that is, 190 ° C. using a capillary flow characteristic tester.
Under the conditions of (1), the ratio (Ds / D) of the nozzle inner diameter D to the diameter (Ds) of the strand extruded from the nozzle having an inner diameter (D) of 2.0 mm and a length of 15 mm at an extrusion speed of 10 mm / min is 1.
It is preferably 3 or more.

The high-pressure radical method low-density polyethylene [B] used in the present invention is a polymerizable monomer such as other α-olefin, vinyl acetate, acrylate, etc., as long as the object of the present invention is not impaired. It may be a copolymer with a monomer.

[Ethylene Copolymer Composition] The ethylene copolymer composition of the present invention comprises the ethylene / α-olefin copolymer [A] and a high pressure radical method low density polyethylene [B]. , The weight ratio ([A]: [B]) of the ethylene / α-olefin copolymer [A] and the high-pressure radical method low-density polyethylene [B] is 99: 1 to 6
Although it is in the range of 0:40, it is preferably in the range of 98: 2 to 70:30, and more preferably in the range of 98: 2 to 80:20.

If the amount of the high-pressure radical method low-density polyethylene [B] is less than the above range, the effect of modifying transparency, melt tension, etc. may be insufficient, and if it is more than the above range, the tensile strength and resistance The stress cracking property and the like may be significantly reduced.

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

The ethylene-based copolymer composition of the present invention can be produced by a known method, for example, the following method. (1) A method of mechanically blending an ethylene / α-olefin copolymer [A] with a high-pressure radical method low-density polyethylene [B], and optionally other components, using an extruder, a kneader, or the like. .

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

(3) Ethylene / α-olefin copolymer [A] and high pressure radical method low density polyethylene [B],
And a method in which other components optionally added are separately dissolved in a suitable good solvent, and then mixed, and then the solvent is removed. (4) A method in which the above methods (1) to (3) are combined.

The ethylene-based copolymer composition of the present invention is processed into a film by ordinary air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooling inflation molding and the like. Obtainable. The film thus formed has excellent transparency and mechanical strength,
It has heat-sealing properties, hot tack properties, heat resistance, good blocking properties, etc., which are the features of ordinary LLDPE.
Further, since the ethylene / α-olefin copolymer [A] has an extremely narrow composition distribution, the film surface is not sticky. Furthermore, since the stress is low even in the high shear region, high-speed extrusion is possible, power consumption is reduced, and it is economically advantageous.

The film obtained by processing the ethylene-based copolymer composition of the present invention is a standard bag, heavy bag, wrap film, raw lami film, sugar bag, oil packaging bag, aquatic packaging bag, food product. It is suitable for various packaging films for packaging, infusion bags, agricultural materials and the like. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester. Furthermore, it can also be used for blow infusion bags, blow bottles, extrusion-molded tubes, pipes, tear-off caps, injection-molded products such as daily sundries, fibers, and large-sized molded products by rotational molding.

[0098]

The ethylene-based copolymer composition of the present invention is
Since the ethylene / α-olefin copolymer [A], which has a narrow composition distribution and good thermal stability, and the high-pressure radical method low-density polyethylene [B] are blended, they have a high melt tension and a high shear range. Excellent formability due to low stress.
From such an ethylene-based copolymer composition, transparency,
A film having excellent mechanical strength, heat sealing property, hot tack property, heat resistance, and blocking resistance can be produced.

[0099]

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

In the present invention, the physical properties of the ethylene copolymer composition are evaluated as follows. [Flow index (FI)] It is defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² . The flow index (FI) is that the resin is extruded from the capillary while changing the shear rate.
It is determined by measuring the stress at that time. That is, using a sample similar to MT measurement, manufactured by Toyo Seiki Seisakusho,
It is measured with a capillary flow characteristic tester at a resin temperature of 190 ° C. and a shear stress range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

The MFR of the resin to be measured (g / 10 minutes)
Change the diameter of the nozzle as follows and measure. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR [Haze] ASTM-D -1003-61.

[Gloss] Measured in accordance with JIS Z8741. [Film Impact] It was measured by a pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisakusho.

[Blocking Power] An inflation film cut into a size of 7 (width) × 20 cm is sandwiched between type papers and sandwiched between glass plates, and a load of 10 kg is applied in an air bath at 50 ° C. for 24 hours. The film was attached to an open jig at a rate of 200 mm / min, the load at this time was set to Ag, and the blocking force F (g / cm) was expressed as F = A / width of test piece. The smaller the value of F, the more difficult the blocking is, that is, the better the blocking resistance is.

[0104]

[Production Example 1] Production of ethylene / α-olefin copolymer [A] [Preparation of catalyst] Silica dried at 250 ° C for 10 hours 6.
After suspending 3 kg with 100 liters of toluene,
Cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 0.96 mol / liter) 41
L was added dropwise over 1 hour. At this time, the temperature in the system is set to 0
It was kept at ℃. Subsequently, the mixture was reacted at 0 ° C. for 60 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended with 125 liters of toluene. To this system, 15 liters of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr = 42.7 mmol / liter) was added at 30 ° C. for 30 minutes, and further reacted at 30 ° C. for 2 hours. It was After that, the supernatant is removed and hexane is added to
By washing twice, a solid catalyst containing 6.2 mg of zirconium per 1 g was obtained.

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

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 18 kg / cm ² -G and a polymerization temperature of 80 ° C. The prepolymerized catalyst prepared above was converted into zirconium atom at 0.15 mmo.
l / h, triisobutylaluminum 10 mmol /
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.020, 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 minutes, the maximum melting point peak in DSC is 116.8 ° C, the melt tension (MT) is 1.5 g, and the decane-soluble part at 23 ° C is 0.02 parts by weight. And the number of unsaturated bonds is 1 carbon atom.
0.09 per 000 and 0.1 per polymer molecule
The number was 6, and the B value showing the distribution state of the α-olefin in the copolymer chain was 1.02.

[0108]

Example 1 [Preparation of Composition] The ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the high-pressure radical method low-density polyethylene (B-2) shown in Table 2 were mixed in a mixing ratio. (A-1 / B
-2) Dry blend at 90/10, and then add tri (2,4-di-t-) as a secondary antioxidant to 100 parts by weight of resin.
0.05 parts by weight of butylphenyl) phosphate, n-octadecyl-3- (4'-hydroxy-) as a heat resistance stabilizer
0.1 parts by weight of 3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added. After that, a conical taper type twin-screw extruder manufactured by Haake Co. was used and kneaded at a set temperature of 180 ° C. to obtain an ethylene copolymer composition.

[Film Processing] Using the ethylene copolymer composition obtained above, an air flow rate of 20 mmφ · L / D = 26 single screw extruder, 25 mmφ die, lip width 0.7 mm, single slit air ring was used. = 90 liters / minute, extrusion rate = 9 g / minute, blow ratio = 1.8, take-up speed = 2.
A film having a thickness of 30 μm was inflation-molded at 4 m / min at a processing temperature of 200 ° C. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0110]

Example 2 Ethylene / α-olefin copolymer (A-
An ethylene-based copolymer composition was prepared in the same manner as in Example 1 except that the mixing ratio (A-1 / B-2) of 1) and the high-pressure radical method low-density polyethylene (B-2) was 75/25. A film having a thickness of 30 μm was prepared in the same manner as in Example 1 using the ethylene copolymer composition prepared above. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0111]

Example 3 In the same manner as in Example 1 except that the high pressure radical method low density polyethylene (B-1) shown in Table 2 was used in place of the high pressure radical method low density polyethylene (B-2). An ethylene-based copolymer composition was prepared, and a film having a thickness of 30 μm was formed in the same manner as in Example 1 using the ethylene-based copolymer composition. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0112]

Reference Example 1 Using the ethylene / α-olefin copolymer (A-1) obtained in Production Example 1, a 30 μm thick film was formed in the same manner as in Example 1. Table 3 shows the melt properties and the film properties.

[0113]

Comparative Example 1 [Production of Ethylene / α-Olefin Copolymer (A-7)] In Production Example 1, instead of bis (n-butylcyclopentadienyl) zirconium dichloride, JP-B-63-
Ethylene / α in the same manner as in Example 1 except that the titanium-based catalyst component described in Japanese Patent No. 54289 was used, triethylaluminum was used in place of methylaluminoxane, and the comonomer content was adjusted as shown in Table 1. -The olefin copolymer (A-7) was produced. Obtained ethylene
Table 1 shows the physical properties of the α-olefin copolymer (A-7).

[Preparation of Composition] The ethylene / α-olefin copolymer (A-7) obtained as described above and Table 2
High Pressure Radical Method Low Density Polyethylene (B-1)
An ethylene copolymer composition was prepared in the same manner as in Example 1 using.

[Film Processing] Using the ethylene-based copolymer composition prepared above, a thickness of 3 was obtained in the same manner as in Example 1.
A 0 μm film was molded. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As shown in Table 3, the obtained film was
Inferior in film impact, wide composition distribution and many solid components, so poor blocking resistance. In addition, comparing Example 3 using Comparative Example 1 with an ethylene / α-olefin copolymer having the same comonomer species and the same MFR and density, Example 3 has a large effect of improving the haze.

[0117]

Comparative Example 2 Using the ethylene / α-olefin copolymer (A-7) obtained in Comparative Example 1, a film having a thickness of 30 μm was formed in the same manner as in Example 1. Table 3 shows the melting characteristics and film physical properties.

[0118]

[Production Examples 2 to 4] Ethylene / α-olefin copolymers (A-2, A-3, and A-olefin copolymer) were produced in the same manner as in Production Example 1 except that the comonomer species and the comonomer content were changed as shown in Table 1.
A-4) was produced. Table 1 shows the physical properties of the obtained ethylene / α-olefin copolymers (A-2, A-3, A-4).

[0119]

Examples 4 to 6 Ethylene / α obtained in Production Examples 2 to 4
-Olefin copolymer (A-2, A-3, A-4) and high-pressure radical method low density polyethylene (B-1) shown in Table 2
An ethylene-based copolymer composition was prepared in the same manner as in Example 1 except that was used, and a film having a thickness of 30 μm was formed in the same manner as in Example 1 using this ethylene-based copolymer composition. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0120]

[Reference Examples 2-4] Ethylene / α obtained in Production Examples 2-4
Using the olefin copolymers (A-2, A-3, A-4), a film having a thickness of 30 μm was formed in the same manner as in Example 1. Table 3 shows the melt properties and the film properties.

[0121]

[Production Examples 5 and 6] In Production Example 1, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride was used in place of bis (n-butylcyclopentadienyl) zirconium dichloride, and comonomer composition was used. The ethylene / α-olefin copolymers (A-5, A-6) were produced in the same manner as in Production Example 1 except that the above was shown in Table 1. The resulting ethylene / α-olefin copolymer (A-
The physical properties of No. 5, A-6) are shown in Table 1.

[0122]

Examples 7 and 8 Ethylene / α obtained in Production Examples 5 and 6
-The ethylene copolymer composition was prepared in the same manner as in Example 1 except that the olefin copolymers (A-5 and A-6) and the high-pressure radical method low-density polyethylene (B-1) shown in Table 2 were used. A film having a thickness of 30 μm was prepared in the same manner as in Example 1 using the ethylene copolymer composition prepared above.
Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

[0123]

[Reference Examples 5 and 6] Ethylene / α obtained in Production Examples 5 and 6
A film having a thickness of 30 μm was formed in the same manner as in Example 1 using the olefin copolymers (A-5 and A-6). Table 3 shows the melt properties and the film properties.

[0124]

Comparative Example 3 The same procedure as in Example 1 was carried out using the ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the high-pressure radical method low density polyethylene (B-3) shown in Table 2. An ethylene-based copolymer composition was prepared, and using this ethylene-based copolymer composition, a thickness of 30 was obtained in the same manner as in Example 1.
A μm film was formed. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As is clear from Comparative Example 3 and Reference Example 1, even when the ethylene / α-olefin copolymer was blended with the high-pressure radical method low-density polyethylene used in Comparative Example 3, the transparency of the film was improved. Less is.

[0126]

Comparative Example 4 The same procedure as in Example 1 was carried out using the ethylene / α-olefin copolymer (A-1) obtained in Production Example 1 and the high pressure radical method low density polyethylene (B-4) shown in Table 2. An ethylene-based copolymer composition was prepared, and using this ethylene-based copolymer composition, a thickness of 30 was obtained in the same manner as in Example 1.
A μm film was formed. Table 3 shows the melt properties and film properties of the ethylene-based copolymer composition.

As is clear from Comparative Example 4 and Reference Example 1, even when the ethylene / α-olefin copolymer was blended with the high-pressure radical method low density polyethylene as used in Comparative Example 4, the melt tension was almost improved. do not do. Further, the transparency of the film is not improved so much.

As is clear from the above examples and reference examples, the blending of the ethylene / α-olefin copolymer with a specific high-pressure radical method low-density polyethylene improves the melt tension and the haze (transparency). Moreover, the ethylene-based copolymer composition according to the present invention has excellent blocking resistance.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Tsutsui 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

[Claims] 1. [A] ethylene and α- having 3 to 20 carbon atoms.
A copolymer with an olefin, wherein (i) the density (d) is in the range of 0.880 to 0.960 g / cm ³ , and (ii)
The melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes, and (iii) the maximum melting point peak (T) in DSC.
(° C)) and the density (d) satisfy the relationship represented by T <400 × d-250, and (iv) the melt tension (MT (g)) and the melt flow rate (M at 190 ° C.
FR) satisfies the relation MT ≦ 2.2 × MFR ^−0.84 , and (v) the decane-soluble part (W (wt%)) and the density (d) at 23 ° C. are MFR ≦ 1.
At 0 g / 10 minutes, W <80 * exp (-100 (d-0.88)) + 0.1 MFR> At 10 g / 10 minutes, W <80 * (MFR-9) ^0.26 * exp (-100 (D-
0.88)) + 0.1, an ethylene / α-olefin copolymer satisfying the relationship, and [B] a low-density polyethylene prepared by a high-pressure radical method, wherein (i) the melt flow rate (MFR) is 0.9. 1-5
Within the range of 0 g / 10 minutes, (ii) the molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MF) measured by GPC.
R) is 7.5 × log (MFR) -1.2 ≦ Mw / Mn ≦ 7.5 × log
(MFR) +12.5, which is a high-pressure radical method low-density polyethylene satisfying the relationship, and the weight ratio of the ethylene / α-olefin copolymer [A] and the high-pressure radical method low-density polyethylene [B] ( [A]: [B]) is in the range of 99: 1 to 60:40, wherein the ethylene copolymer composition is characterized.