JPH06329848A - Ethylenic copolymer composition - Google Patents

Abstract

(57) [Summary] [Structure] An ethylene / α-olefin copolymer composition comprising ethylene / α-olefin copolymers [A] and [B] having specific physical properties and different densities and MFRs. An ethylene-based copolymer composition prepared by blending a high-pressure radical method low-density polyethylene having specific physical properties. [Effect] It is possible to produce a film having excellent moldability, transparency, mechanical strength, and blocking resistance.

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 thermal stability and moldability as compared with a conventionally known ethylene-based copolymer or an ethylene-based copolymer composition. The present invention relates to an ethylene-based copolymer composition capable of producing a film excellent in transparency, mechanical strength and blocking resistance.

[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 under extrusion under high shear is small from the economical viewpoint such as quality improvement of the molded article and reduction of power consumption during molding.

By the way, a method of 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 Japanese Patent Laid-Open No. 56-90810. Japanese Patent Laid-Open No. 60-106806 and the like. 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.

Among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts are 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 product 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 excellent melt tension, small stress in the high shear region, good thermal stability, excellent mechanical strength, and narrow composition distribution appears, its industrial use will be improved. The target value is extremely large.

As a result of intensive studies in view of such a situation, the present inventors have found that (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 a carbon number of 3 to 20
Ethylene obtained by copolymerizing with α-olefin
It was found that the α-olefin copolymer is excellent in melt tension and thermal stability and has a narrow composition distribution. However, such an ethylene / α-olefin copolymer does not always have a good balance between melt tension and fluidity, and thus a problem may occur when it is extrusion-molded into a film. Then, as a result of further research, two kinds of ethylene / α-obtained by using the above catalyst, which have different densities and MFRs, were obtained.
The ethylene-based copolymer composition obtained by further blending the ethylene / α-olefin copolymer composition obtained by blending the olefin copolymer with low-density polyethylene by the high-pressure radical method has thermal stability, The film obtained is excellent in melt tension and fluidity (FI) in a high shear region, and the obtained film has transparency, mechanical strength,
The inventors have found that they have excellent blocking resistance and have completed the present invention.

[0008]

It is an object of the present invention to provide an ethylene copolymer composition capable of producing a film which is excellent in heat stability and moldability, transparency, mechanical strength and blocking resistance. It is an object.

[0009]

SUMMARY OF THE INVENTION An ethylene-based copolymer composition according to the present invention is a copolymer of [I] (A-i) ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A- ii) The density (d) is in the range of 0.880 to 0.940 g / cm ³ , and (A-ii
i) The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is in the range of 1.0 to 10.0 dl / g, and (A-iv) of the endothermic curve measured by a differential scanning calorimeter (DSC). The temperature (Tm (° C.)) at the maximum peak position and the density (d) satisfy the relationship represented by Tm <400 × d-250, and (A-v) melt tension (MT (g)) at 190 ° C. and melt Flow rate (MFR)
^Satisfy the relation expressed by MT ≦ 2.2 × MFR ^−0.84 , and (A-vi) the decane-soluble part (W (wt%)) at room temperature and the density (d) are W <80 × exp (− 100 (d-0.88)) + 0.1 satisfying the relationship represented by ethylene / α-olefin copolymer [A] 5 to 95% by weight, (Bi) ethylene, and 3 to 20 carbon atoms A copolymer with α-olefin,
(B-ii) Density (d) is 0.910 to 0.960 g / cm ^3.
(B-iii), the intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is in the range of 0.5 to 2.0 dl / g, and (B-iv) the differential scanning calorimeter ( Temperature at the maximum peak position of the endothermic curve measured by DSC (Tm (° C))
And the density (d) satisfy the relationship represented by Tm <400 × d-250, and (B-v) the decane-soluble part (W (wt%)) at room temperature and the density (d) have MFR ≦ 10.
When g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (-100 (D-
0.88)) + 0.1, wherein the ethylene / α-olefin copolymer composition [B] is 5 to 95% by weight, and the ethylene / α-olefin copolymer composition comprises (i) The ratio ([A] / [B]) between the density of the ethylene / α-olefin copolymer [A] and the density of the ethylene / α-olefin copolymer [B] is less than 1, ) The ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] is 1 or more. And (iii) the density of the composition is in the range of 0.890 to 0.955 g / cm ³ , and (iv) the melt flow rate (MFR) of the composition at 190 ° C. and a load of 2.16 kg is 0. .1-10
An ethylene / α-olefin copolymer composition having a range of 0 g / 10 minutes, and [II] a low density polyethylene by a high pressure radical method, wherein (i) the melt flow rate (MFR) is 0.1 to 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, which satisfies the relationship, and the weight of the above ethylene / α-olefin copolymer composition [I] and the above-mentioned high-pressure radical method low-density polyethylene [II]. Ratio ([I]: [II]) is 99: 1 to 6
It is characterized by being in the range of 0:40.

Such an ethylene-based copolymer composition is
It is possible to produce a film having excellent heat stability and moldability, transparency, mechanical strength, and blocking resistance.

[0011]

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 composed of an ethylene / α-olefin copolymer [A] and an ethylene / α-olefin copolymer [B], and a high pressure. It is formed from low density polyethylene by the radical method.

[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] has the following characteristics (A-ii) to (A-vi). (A-ii) Density (d) is 0.880 to 0.940 g / cm
³ , preferably 0.890 to 0.935 g / cm ³ , and more preferably 0.900 to 0.930 g / cm ³ .

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.

(A-iii) The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is 1.0 to 10.0 dl / g, preferably 1.25 to 8 dl / g, more preferably 1.27.
It is preferably in the range of ˜6 dl / g.

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

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(° C) is 10 ° C /
It is obtained from the endothermic curve when the temperature is raised to 200 ° C. in minutes, 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. For the measurement, a DSC-7 type device manufactured by Perkin Elmer was used.

( ^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 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, tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was previously added to the ethylene / α-olefin copolymer in an amount of 0.0
5% by weight, n-octadecyl-3- (4'- as a heat stabilizer
Hydroxy-3 ', 5'-di-t-butylphenyl) propionate was added in an amount of 0.1% by weight, and calcium stearate as a hydrochloric acid absorbent was added in an amount of 0.05% by weight.

(A-vi) The n-decane soluble component amount fraction (W (wt%)) and the density (d) at room temperature are 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 is satisfied.

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

The relationship between the temperature (Tm) at the maximum peak position and the density (d) in the endothermic curve thus measured by the differential scanning calorimeter (DSC), and the n-decane soluble component amount fraction (W) It can be said that the ethylene / α-olefin copolymer [A] used in the present invention, which has the above 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 unsaturated bond is quantified 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.

Ethylene / α-having the above characteristics
The olefin copolymer [A] is a catalyst for olefin polymerization, which is formed from (a ') transition metal compound, (b) organoaluminum oxy compound and (c) carrier described below, and (d) organoaluminum compound if necessary. In the presence of ethylene, an α-olefin having 3 to 20 carbon atoms is copolymerized so that the resulting copolymer has a density of 0.880 to 0.940 g / cm ^3. it can.

[Ethylene / α-olefin copolymer [B]] The ethylene / α-olefin copolymer [B] 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 [B]
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 ethylene / α-olefin copolymer [B] has the following characteristics (B-ii) to (B-vi). (B-ii) Density (d) is 0.910 to 0.960 g / cm
³ , preferably 0.915 to 0.955 g / cm ³ , and more preferably 0.920 to 0.950 g / cm ³ .

(B-iii) The intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is 0.5 to 2.0 dl / g, preferably 0.55 to 1.9 dl / g, and more preferably 0. .6
It is preferably in the range of to 1.8 dl / g.

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

(B-v) Melt tension (MT (g)) and melt flow rate (MFR) satisfy the relationship expressed as ^MT≤2.2 × MFR- ^0.84 .

(B-vi) The n-decane-soluble component amount fraction (W (wt%)) 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 minutes, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

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

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

Ethylene / α-having the above characteristics
The olefin copolymer [B] has the following (a ′)
In the presence of a transition metal compound, (b) an organoaluminum oxy compound and (c) a carrier, and optionally (d) an organoaluminum compound-forming catalyst for olefin polymerization, ethylene and α- having 3 to 20 carbon atoms are used. With olefins,
The density of the obtained copolymer is 0.910 to 0.960 g / c.
It can be produced by copolymerizing so as to have m ³ .

The ethylene / α-olefin copolymer [A], which constitutes the ethylene copolymer composition of the present invention,
A catalyst component used in the copolymerization of [B] (a)
A transition metal compound of Group iv of the periodic table containing a ligand having a cyclopentadienyl skeleton, (a ') a transition metal compound of Group iv of the periodic table containing a ligand having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound,
The carrier (c) and the organoaluminum compound (d) will be specifically described.

The transition metal compound (a) used in the present invention (hereinafter sometimes referred to as "component (a)") is a transition metal compound represented by the following formula [I]. ML ¹ x ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the periodic table, and L ¹ is a ligand that coordinates with the transition metal atom M. At least two ligands L ¹
Is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group or a carbon number 3
10 is a substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups, wherein the ligand L other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy group. A group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and 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 ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are
Cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group or C3 to C1
0 is a substituted cyclopentadienyl group having at least one substituent selected from hydrocarbon groups, and the ligand L ¹ other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
Is 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. 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, an alkyl group is preferable, and an n-propyl group and an 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 ¹ 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 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, 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.

In the present invention, the periodic table containing a ligand (a ') having a cyclopentadienyl skeleton, which is used in the copolymerization of the ethylene / α-olefin copolymer [B],
The Group IV transition metal compound (hereinafter sometimes referred to as “component (a ′)”) is a Group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton. Although not particularly limited, a transition metal compound represented by the following general formula [III] is preferable.

ML _x ... [III] [wherein M is a transition metal selected from Group IVB of the periodic table, L is a ligand that coordinates to the transition metal, and at least one L is cyclo). L is a ligand having a pentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a trialkylsilyl group, an SO ₃ R group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom, and x is a transition It is the valence of the metal. ] The transition metal compound represented by the general formula [III] includes the transition metal compound (bI) represented by the general formula [I] and the transition metal compound (b- represented by the general formula [II]. II) is included.

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

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

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [III] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are alkylene such as ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

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

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

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

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

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

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

It is also possible to use a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above. As the compound (a ′) used in the present invention, the above-exemplified compounds can be used as a catalyst, but it is preferable to use the compound of the transition metal compound (a) described above as a catalyst. Particularly preferably used compounds are more preferable as the catalyst. Further, it is particularly desirable to use a compound in which the compounds (a ′) and (a) are the same.

Next, the organoaluminum 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, and can be used in JP-A-2- 27
It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent No. 6807.

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 dissolved in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 times that 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) (hereinafter sometimes referred to as "component (c)") used in the present invention is an inorganic or organic compound, and has a particle size of 10 to 300 μm, preferably 20 to 300 μm. 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 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 manufacturing 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 is formed from the above-mentioned (a) transition metal compound, (b) organoaluminum oxy compound and (c) carrier, and if necessary (d)
Organoaluminum compounds may be used.

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

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

Such an organoaluminum compound (d)
Specifically, the following compounds 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 [V] can be used. R ¹ _n AlY _3-n ... [V] (In the formula [V], R ¹ is the same as above, and Y is -OR.
² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) 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 ; (6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN
(Et) Al (iso-Bu) ₂ Among the organoaluminum compounds represented by the above general formulas [IV] and [V], the general formulas R ¹ ₃ Al and R ¹ _n Al (OR ² )
_The compounds represented by _3-n and R ¹ _n Al (OAlR 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 copolymers [A] and [B] are produced, the above-mentioned component (a), component (b) and component (c), and if necessary, A catalyst prepared by contacting the component (d) is used. 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 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, 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 catalyst used in the production of the olefin copolymers [A] and [B] has 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom of the transition metal atom derived from the component (a) per 1 g of the component (c). It is preferably supported in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ gram atom, and 10 ^{−3 to} 5 × 10 ⁻² aluminum atoms derived from the component (b) and the component (d) per 1 g of the component (c). It is desirable to support gram atoms, preferably in an amount of 2 × 10 ⁻³ to 2 × 10 ⁻² gram atoms.

The catalyst used in the production of the ethylene / α-olefin copolymers [A] and [B] is the above-mentioned component (a), component (b), component (c) and, if necessary, a component. It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of (d). 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 (a) 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. Then, the preliminarily polymerized catalyst can be obtained by adding the solid catalyst component obtained above to an inert hydrocarbon containing an organoaluminum compound (component (d)) and introducing an olefin therein.

The olefin polymer produced by the prepolymerization is
0.1-500 g, preferably 0.2 per 1 g of carrier (c)
It is desirable that the amount is ˜300 g, more preferably 0.5 to 200 g. Further, in the prepolymerization catalyst, the component (a) as a transition metal atom is about 5 × per 1 g of the carrier (c).
10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2
The aluminum atom (Al) derived from the component (b) and the component (d), which is supported in an amount of × 10 ⁻⁴ gram atom, has a molar ratio (Al / A) to the transition metal atom (M) derived from the component (a). M), 5-200, preferably 10-150
It is desirable that the particles are supported in an amount in the range.

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 the concentration of the transition metal atom in the polymerization reaction system in the range of 10 ^-8 to 10 ^-3 g 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 from normal 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.

When the ethylene / α-olefin copolymer [A] used in the present invention is produced by a slurry polymerization method, the polymerization temperature is usually -50 to 90 ° C, preferably 0.
When produced by a gas phase polymerization method in the range of -80 ° C,
It can be obtained by copolymerization under the condition that the polymerization temperature is usually 0 to 90 ° C, preferably 20 to 80 ° C.

When the ethylene / α-olefin copolymer [B] used in the present invention is produced by the slurry polymerization method, the polymerization temperature is usually -30 to 100 ° C, preferably 20 to 90 ° C. When producing by a gas phase polymerization method, the polymerization temperature is usually 20 to 120 ° C., preferably 40 to 120 ° C.
It can be obtained by copolymerization under the conditions of 100 ° C.

[Ethylene / α-olefin Copolymer Composition] The ethylene / α-olefin copolymer composition comprises the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [A]. B] and the ethylene / α-olefin copolymer [A] is contained in an amount of 5 to 95% by weight, preferably 10 to 90% by weight.
-The olefin copolymer [B] is contained in an amount of 5 to 95% by weight, preferably 10 to 90% by weight.

Ethylene / α-olefin copolymer [A]
And ethylene / α-olefin copolymer [B] are the ratio of the density of ethylene / α-olefin copolymer [A] to the density of ethylene / α-olefin copolymer [B] ([A ] / [B]) is less than 1, preferably 0.930-
Used in combination so as to be 0.999. The ratio of the ethylene · alpha-olefin copolymer intrinsic viscosity [eta _A] of [A], and the intrinsic viscosity [eta _B] of the ethylene · alpha-olefin copolymer _{[B] ([η A]} / [Η _B ])
Is 1 or more, preferably 1.05 to 10, more preferably 1.1 to 5 in combination.

Such an ethylene / α-olefin copolymer composition has a density of 0.890 to 0.955 g / c.
m ^3, preferably in the range of 0.900~0.950g / cm ^3, MFR is 0.1 to 100 g / 10 min, it is desirable that preferably in the range of 0.2 to 50 g / 10 min.

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

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

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

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

[High Pressure Radical Method Low Density Polyethylene] Next, the high pressure radical method low density polyethylene used in the present invention will be specifically described.

High-pressure radical method low-density polyethylene is polyethylene with many branches having long-chain branches produced by so-called high-pressure radical polymerization, and ASTM D1238-
MFR measured under 65T at 190 ° C. under a load of 2.16 kg is 0.1 to 50 g / 10 minutes, preferably 0.2
-10g / 10min, more preferably 0.2-8g / 10
It is desirable to be in the range of minutes.

The high-pressure radical method low-density polyethylene according to the present invention has an index (Mw) of the molecular weight distribution 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 is GPC-150C manufactured by Millipore.
Was measured as follows. Separation column is T
SK GNH HT, column size is 72m in 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.

Further, the high-pressure radical method low-density polyethylene according to the present invention has a swell ratio representing the degree of long-chain branching,
That is, using a capillary flow characteristic tester, the diameter (D) of a strand extruded at a extrusion rate of 10 mm / min from a nozzle having an inner diameter (D) of 2.0 mm and a length of 15 mm under conditions of 190 ° C
It is desirable that the ratio (Ds / D) between the s) and the nozzle inner diameter D is 1.3 or more.

The high-pressure radical method low density polyethylene used in the present invention may be combined with other polymerizable monomers such as α-olefins, vinyl acetate and acrylate as long as the object of the present invention is not impaired. It may be a copolymer of

[Ethylene Copolymer Composition] The ethylene copolymer composition of the present invention comprises the ethylene / α-olefin copolymer composition [A] and the ethylene / α-olefin copolymer composition. Ethylene / α- consisting of the product [B]
An olefin copolymer composition [I] and a low-density polyethylene [II] produced by the high-pressure radical method, and an ethylene / α-olefin copolymer composition [I] and a high-pressure radical low-density polyethylene [II]. And the weight ratio ([I]:
[II]) is in the range of 99: 1 to 60:40, but 9
It is preferably in the range of 8: 2 to 70:30, and 9
It is more preferably in the range of 8: 2 to 80:20.

When the amount of the high-pressure radical method low-density polyethylene is less than the above range, the effect of modifying transparency and melt tension may be insufficient, and when it is more than the above range, the tensile strength and the stress crack resistance may be poor. Etc. may decrease significantly.

Such an ethylene-based copolymer composition is
It can be produced using a known method, for example, the following method. (1) A method of mechanically blending an ethylene / α-olefin copolymer composition, a high-pressure radical method low-density polyethylene, and optionally other components, using an extruder, a kneader, or the like.

(2) The ethylene / α-olefin copolymer composition, the high-pressure radical method low-density polyethylene, and other components optionally added are mixed with a suitable good solvent (for example;
A solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then removing the solvent.

(3) Ethylene / α-olefin copolymer composition, high-pressure radical method low-density polyethylene, and optionally other components added are separately dissolved in a suitable good solvent to prepare a solution, which is then mixed. 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, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, within a range that does not impair the object of the present invention. Additives such as pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, and antioxidants may be blended as necessary.

The ethylene 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 formed in this way has excellent mechanical strength and
It has heat sealing properties, hot tack properties, heat resistance, good blocking properties, etc., which are the characteristics of LDPE. Also,
Since the composition distribution of the ethylene / α-olefin copolymers [A] and [B] is extremely narrow, the film surface is not sticky. Furthermore, since the stress is low even in the high shear region, high-speed extrusion is possible, power consumption is reduced, and it is economically advantageous.

The film obtained by processing the ethylene-based copolymer composition of the present invention is a standard bag, heavy bag, wrap film, raw lami film, sugar bag, oil packaging bag, water 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. Further, it can 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.

[0122]

The ethylene-based copolymer composition of the present invention is
A high pressure radical method low density polyethylene is blended with an ethylene / α-olefin copolymer composition comprising ethylene / α-olefin copolymers [A] and [B] having specific physical properties and different densities and MFRs. Therefore, it is possible to produce a film which is excellent in heat stability and moldability, and is excellent in transparency, mechanical strength, and blocking resistance.

[0123]

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 and the film 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.

[Film Impact] The film impact was measured with 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, 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.

[0128]

[Production Example 1] Production of ethylene / α-olefin copolymer [A-1] [Preparation of catalyst component] 10.0 kg of silica dried at 250 ° C for 10 hours was suspended in 154 liters of toluene, Cooled to 0 ° C. Then, 57.5 liters of a toluene solution of methylaluminoxane (Al = 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and reacted at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene. To this system, a solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride in toluene (Zr = 27.0 mm
ol / l) (16.8 l) was added dropwise at 80 ° C. over 30 minutes, and the reaction was continued at 80 ° C. for 2 hours. Then, the supernatant was removed and the solid was washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst] 870 g of the solid catalyst obtained above and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and ethylene preparatory was carried out at 35 ° C. for 5 hours. By carrying out the polymerization, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[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 75 ° C. 0.15 mmol of the prepolymerized catalyst prepared above in terms of zirconium atom
/ H, triisobutylaluminum 10 mmol / h
Of ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
034, hydrogen / ethylene = 1.7 × 10 ⁻⁴ , ethylene concentration = 20%).

The yield of the ethylene / α-olefin copolymer (A-1) obtained was 5.8 kg / h, the density was 0.908 g / cm ³ , and the MFR was 0.77 g / 10.
The temperature at the maximum peak position of the endothermic curve measured by DSC is 93.6 ° C, the decane-soluble part at 23 ° C is 0.51% by weight, and the number of unsaturated bonds is 1000 carbon atoms. The number was 0.08 per molecule and 0.70 per molecule of polymer.

[0132]

Example 1 [Preparation of Ethylene / α-Olefin Copolymer Composition] The ethylene / α-olefin copolymer (A-1) (density: 0.908 g / cm ³ ) obtained in Production Example 1 was used. The ethylene / α-olefin copolymer (B-1) (density: 0.938 g / cm ³ ) produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1 Melt-kneading at a ratio (A-1 / B-1) of 60/40 to produce ethylene / α-
An olefin copolymer composition (L-1) was obtained.

Table 2 shows the physical properties of the ethylene / α-olefin copolymer composition (L-1) thus obtained. [Preparation of ethylene-based copolymer composition] This ethylene / α
-Olefin copolymer composition (L-1) and high pressure radical method low density polyethylene (H-1) shown in Table 3 were dry blended at a mixing ratio (L-1 / H-1) of 90/10, Furthermore, tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to 0.05 parts by weight per 100 parts by weight of the resin.
Parts by weight, 0.1 parts by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate as a heat resistance stabilizer, and 0 parts by weight of calcium stearate as a hydrochloric acid absorbent. 0.05 parts by weight was compounded. Then, using a conical taper twin-screw extruder manufactured by Haake Co., set temperature 18
The mixture was kneaded at 0 ° C. to obtain an ethylene copolymer composition.

[Film Processing] Using the obtained ethylene-based copolymer composition, using a single screw extruder of 20 mmφ · L / D = 26, a 25 mmφ die, a lip width of 0.7 mm, and a single slit air ring, Air flow rate = 90 liters /
A film having a thickness of 30 μm was inflation-molded under the following conditions: min, extrusion rate = 9 g / min, blow ratio = 1.8, take-up speed = 2.4 m / min, processing temperature = 200 ° C.

The melt properties and film properties of the ethylene copolymer composition are shown in Table 4.

[0136]

Reference Example 1 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-1) produced in Example 1, Example 1
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-1). From Example 1 and Reference Example 1, it is understood that the blending of the high-pressure radical method low-density polyethylene improved the melt tension and the fluidity in the high shear region, and also improved the transparency of the obtained film.

[0138]

Example 2 [Preparation of Ethylene / α-Olefin Copolymer Composition]
Production example except that the monomer content was adjusted as shown in Table 1.
Ethylene / α-olefin copolymer weight produced in the same manner as in No. 1
Combined (A-2) (Density: 0.909 g / cm³) And Eti
Ren / α-olefin copolymer (B-2) (density: 0.9
43 g / cm ³) And weight ratio (A-2 / B-2) 70/30
Melt and knead with ethylene / α-olefin copolymer composition
The thing (L-2) was obtained. Ethylene / α-olefin copolymerization
Table 2 shows the physical properties of the body composition (L-2).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-2) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, a thickness of 30 μm was obtained in the same manner as in Example 1.
Was formed into a film.

Table 4 shows melt properties and film properties of the ethylene-based copolymer composition.

[0142]

Reference Example 2 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-2) produced in Example 2, Example 1 was used.
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-2). From Example 2 and Reference Example 2, it can be seen that blending the high-pressure radical method low-density polyethylene improved the melt tension and the fluidity in the high shear region, and also improved the transparency of the obtained film.

[0144]

Example 3 [Preparation of Ethylene / α-Olefin Copolymer Composition]
Production example except that the monomer content was adjusted as shown in Table 1.
Ethylene / α-olefin copolymer weight produced in the same manner as in No. 1
Combined (A-3) (Density: 0.910 g / cm³) And Eti
Ren / α-olefin copolymer (B-3) (density: 0.9
46 g / cm ³) And the weight ratio (A-3 / B-3) 60/40
Melt and knead with ethylene / α-olefin copolymer composition
The thing (L-3) was obtained. Ethylene / α-olefin copolymerization
Table 2 shows the physical properties of the body composition (L-3).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-3) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, in the same manner as in Example 1, the thickness was 30 μm.
Was formed into a film.

Table 4 shows melt properties and film properties of the ethylene-based copolymer composition.

[0148]

Reference Example 3 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-3) produced in Example 3, Example 1 was used.
A film having a thickness of 30 μm was formed in the same manner as in.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-3). From Example 3 and Reference Example 3, by blending the high-pressure radical method low-density polyethylene, the melt tension of the composition and the fluidity in the high shear region were improved, and the transparency of the obtained film was improved. Recognize.

[0150]

Comparative Example 1 [Preparation of Ethylene / α-Olefin Copolymer Composition] In Production Example 1, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride was used instead of JP-B-63-54289. Ethylene produced in the same manner as in Production Example 1 except that the titanium-based catalyst component described in JP-A No. 1993-242242 was used, triethylaluminum was used in place of methylaluminoxane, and the gas composition ratio was changed as shown in Table 1. α-olefin copolymer (A-4) (density: 0.915 g / c
m ³ ) and an ethylene / α-olefin copolymer (B-4)
(Density: 0.933 g / cm ³ ) to weight ratio (A-4 / B-4)
It was melt-kneaded at 60/40 to obtain an ethylene / α-olefin copolymer composition (L-4). Table 2 shows the physical properties of the ethylene / α-olefin copolymer composition (L-4).

[Preparation of Ethylene Copolymer Composition] An ethylene copolymer composition was prepared in the same manner as in Example 1 except that the ethylene / α-olefin copolymer composition (L-4) was used. Obtained.

[Film Processing] Using the obtained ethylene-based copolymer composition, a thickness of 30 μm was obtained in the same manner as in Example 1.
Was formed into a film.

The melt properties and film properties of the ethylene copolymer composition are shown in Table 4. The obtained film was compared with Example 1 using the ethylene / α-olefin copolymer composition (L-1) having the same density and MFR,
It can be seen that the obtained film is inferior in transparency and film impact.

[0154]

Comparative Example 2 [Film Processing] Using the ethylene / α-olefin copolymer composition (L-4) obtained in Comparative Example 1, a film having a thickness of 30 μm was formed in the same manner as in Example 1.

Table 4 shows the melt properties and film properties of the ethylene / α-olefin copolymer composition (L-4). From Comparative Example 1 and Comparative Example 2, Comparative Example 1 corresponds to Example 1
It can be seen that the obtained film has less improvement in transparency as compared with.

[0156]

Comparative Example 3 [Preparation of Ethylene Copolymer Composition] An ethylene / α-olefin copolymer (C-1) produced in the same manner as in Production Example 1 except that the comonomer content was adjusted as shown in Table 1. )
An ethylene-based copolymer composition was obtained in the same manner as in Example 1 except that was used.

[Film Processing] Using the obtained ethylene-based copolymer composition, in the same manner as in Example 1, the thickness was 30 μm.
Was formed into a film.

Table 4 shows melt properties and film properties of the ethylene copolymer composition. The ethylene-based copolymer composition obtained in Comparative Example 3 has the same MFR as in Example 3.
The ethylene / α-olefin copolymer has a lower fluidity in the high shear region than that of the ethylene-based copolymer composition and has the same density and MFR as those of the ethylene / α-olefin copolymer (C-1). It can be seen that the obtained film is inferior in film impact as compared with the ethylene-based copolymer composition of Example 1 using the combined composition (L-1).

[0159]

[Table 1]

[0160]

[Table 2]

[0161]

[Table 3]

[0162]

[Table 4]

 ─────────────────────────────────────────────────── ─── 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. [I] (A-i) ethylene and 3 to 3 carbon atoms
A copolymer of 20 α-olefins (A-ii)
The density (d) is in the range of 0.880 to 0.940 g / cm ³ , and the intrinsic viscosity [η _A ] measured in decalin at (A-iii) 135 ° C. is 1.0 to 10.0 dl / g. (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 shown by Tm <400 × d-250. (A-v) melt tension (MT (g)) and melt flow rate (MFR) at 190 ° C
^Satisfy the relation expressed by MT ≦ 2.2 × MFR ^−0.84 , and (A-vi) the decane-soluble part (W (wt%)) at room temperature and the density (d) are W <80 × exp (− 100 (d-0.88)) + 0.1 satisfying the relationship represented by ethylene / α-olefin copolymer [A] 5 to 95% by weight, (Bi) ethylene, and 3 to 20 carbon atoms A copolymer with α-olefin,
(B-ii) Density (d) is 0.910 to 0.960 g / cm ^3.
(B-iii), the intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is in the range of 0.5 to 2.0 dl / g, and (B-iv) the differential scanning calorimeter ( Temperature at the maximum peak position of the endothermic curve measured by DSC (Tm (° C))
And the density (d) satisfy the relationship represented by Tm <400 × d-250, and (B-v) the decane-soluble part (W (wt%)) at room temperature and the density (d) have MFR ≦ 10.
When g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (-100 (D-
0.88)) + 0.1, wherein the ethylene / α-olefin copolymer composition [B] is 5 to 95% by weight, and the ethylene / α-olefin copolymer composition comprises (i) The ratio ([A] / [B]) between the density of the ethylene / α-olefin copolymer [A] and the density of the ethylene / α-olefin copolymer [B] is less than 1, ) The ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of the ethylene / α-olefin copolymer [A] to the intrinsic viscosity of the ethylene / α-olefin copolymer [B] is 1 or more. And (iii) the density of the composition is in the range of 0.890 to 0.955 g / cm ³ , and (iv) the melt flow rate (MFR) of the composition at 190 ° C. and a load of 2.16 kg is 0. .1-10
An ethylene / α-olefin copolymer composition having a range of 0 g / 10 minutes, and [II] a low density polyethylene by a high pressure radical method, wherein (i) the melt flow rate (MFR) is 0.1 to 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, which satisfies the relationship, and the weight of the above ethylene / α-olefin copolymer composition [I] and the above-mentioned high-pressure radical method low-density polyethylene [II]. Ratio ([I]: [II]) is 99: 1 to 6
An ethylene-based copolymer composition characterized by being in the range of 0:40.