JPH0995572A - Ethylene polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene polymer compsn. which is excellent in moldability and can give a molded item excellent in mechanical strengths and stiffness by compounding two ethylene polymers of which at least one is produced with a metallocene catalyst. SOLUTION: This compsn. is prepd. by compounding 20-90wt.% ethylene hompolymer or an ethylene-(3-20C) α-olefin copolymer having a density of 0.96-0.98g/cm<3> and an intrinsic viscosity [η] of 0.5-3.0dl/g with 80-10wt.% ethylene homopolymer or an ethylene-(3-20C) α-olefin copolymer having a density of 0.91-0.965g/cm<3> and an intrinsic viscosity of 1.0-10dl/g, at least one of those two polymers being produced by using a metallocene catalyst and the ratio of the density of the former polymer to the latter being higher than 1. The compsn. has a density of 0.940-0.970g/cm<3> , a melt flow rate (MFR) of 0.005-20g/10min, and a die swell ratio higher than 1.35 and satisfies the relation: log(melt tension)>=-0.4log(MFR)+0.7.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene polymer composition having high melt tension and diameter swell ratio, and excellent mechanical strength and rigidity.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene polymer, ethylene / α-
Ethylene polymers such as olefin copolymers have been conventionally molded by various molding methods such as blow molding, vacuum / pressure molding, calendar molding, inflation molding, extrusion molding, foam molding, stretched film molding, and injection molding.
It is used for a wide range of purposes.

Such an ethylene polymer is required to have various properties depending on the use or the molding method. For example, when a film is produced by high-speed inflation molding, the ethylene polymer having a large melt tension (melt tension) is used. It is necessary to use merging to prevent the shaking and tearing of bubbles. When manufacturing industrial cans, drums, bottles, etc. by blow molding, improve the pinch-off shape,
Further, in order to obtain a blow molded product having a narrow wall thickness distribution, it is necessary to use an ethylene polymer having a large swell ratio (diameter swell ratio). Blow-molded products are usually required to have properties such as impact strength, but in recent years, in addition to these properties, improvement in rigidity has also been required to improve durability and economy.

By the way, ethylene-based polymers have been
It is produced using a catalyst such as an i-based catalyst or a Cr-based catalyst (Phillips type catalyst), or is produced by a high pressure method. Of these, Ti-based catalysts, especially MgCl
₂ Ethylene polymer produced using Ziegler-Natta type catalyst represented by supported Ti type catalyst has a molecular structure with almost no long chain branching, and has excellent rigidity and impact resistance. However, it is inferior in moldability to the ethylene polymer produced by the Cr catalyst. On the other hand, the ethylene-based polymer produced by the high pressure method and the ethylene-based polymer produced by the Cr-based catalyst have higher melt tension and swell ratio than the ethylene-based polymer produced by the Ziegler-Natta type catalyst,
It has excellent moldability, but has a molecular structure with long-chain branching, and is inferior in rigidity and impact resistance.

[0005] Various methods have been proposed for improving the properties of such ethylene polymers. For example, JP-A-55-12735 proposes a blend of polyethylene produced by a Ziegler-Natta type catalyst and polyethylene produced by a high pressure method. JP-A-60-36546 discloses polyethylene produced with a Ziegler-Natta type catalyst and C
Blends with polyethylene produced with r-based catalysts have been proposed. However, these polyethylene blends have improved moldability, but are inferior in rigidity and impact resistance, as compared with ethylene-based polymers produced with a Ziegler-Natta type catalyst.

The present inventor has studied the ethylene-based polymer in view of the above-mentioned prior art. As a result, it is composed of a specific high-density ethylene-based polymer and a specific ethylene-based polymer, and at least one of them is a metallocene catalyst. It has been found that the ethylene-based polymer composition produced by using the above-mentioned resin and having a density ratio of more than 1 is excellent in moldability, stress crack resistance, mechanical strength, rigidity and the like. It has been found that the composition can be molded into a wide variety of products by various molding methods such as blow molding, vacuum / pressure molding, calender molding, inflation molding, extrusion molding, foam molding, stretched film molding and injection molding. The present invention has been completed.

[0007]

OBJECT OF THE INVENTION The present invention has excellent moldability, blow molding,
Various molding methods such as vacuum / pressure molding, calender molding, inflation molding, extrusion molding, foam molding, stretched film molding, injection molding, etc. can be used to mold products for a wide range of applications, and it has excellent mechanical strength and rigidity. It is an object of the present invention to provide an ethylene polymer composition capable of obtaining a molded product.

[0008]

SUMMARY OF THE INVENTION The first ethylene-based polymer composition according to the present invention comprises (A) an ethylene polymer or ethylene and 3 carbon atoms.
A copolymer of 20 to 20 α-olefins (A-1)
The density (d _A ) is in the range of 0.96 to 0.98 g / cm ³ , and (A-2) the intrinsic viscosity [η] is 0.5 to 3.0 dl / g.
20 to 90% by weight of the ethylene polymer in the range of (B) ethylene polymer or ethylene and 3 carbon atoms
A copolymer of 20 to 20 α-olefins (B-1)
The density (d _B ) is in the range of 0.91 to 0.965 g / cm ³ , and (B-2) the intrinsic viscosity [η] is 1.0 to 10 dl / g.
In the range of 80 to 10% by weight, wherein at least one of the (A) ethylene polymer and the (B) ethylene polymer is an ethylene-based polymer produced using a metallocene catalyst. a coalescing, (1) the (a) than the the density of the ethylene polymer (d _a) (B) ratio of the density (d _B) of the ethylene-based polymer (d _a / d _B) is 1 Large (2) Density 0.940-0.970g /
in the range of cm ³ , (3) Melt flow rate (MF
R: 190 ° C., measured under 2.16 kg load) is 0.005
The melt flow rate (MFR) and melt tension (MT) are in the range of log (MT).
≧ −0.4 log (MFR) +0.70 (5) It is characterized in that the diameter swell ratio exceeds 1.35.

The ethylene polymer (A) and / or the ethylene polymer (B) as described above can be produced, for example, by using the following metallocene catalyst. [I] a transition metal compound represented by the following general formula (I),

[0010]

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(In the formula, M represents a transition metal atom of Groups 4 to 6 of the Periodic Table, R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and are hydrogen atoms, Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group Or some of the groups adjacent to each other may be bonded to each other to form at least one ring together with the carbon atom to which those groups are bonded, X ¹ and X ² may be the same or different from each other. , A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, and Y is A divalent hydrocarbon group, a divalent silicon-containing group or Indicating the valency of germanium-containing group.) [II] a transition metal compound compound capable of activating the [I], and (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

Further, the ethylene polymer (A) and / or the ethylene polymer (B) as described above can be produced by using the following metallocene catalyst. [I] a transition metal compound represented by the following general formula (II) or a transition metal compound represented by the following general formula (III),

[0013]

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(In the formula, M, X ¹ and X ² are the same as those in the general formula (I), and R ^{5 to} R ⁹ may be the same or different from each other, and at least two of them are methyl. Or ethyl and the other is hydrogen atom, R ¹⁰ ~
R ¹⁴ may be the same or different, and at least two of them are methyl or ethyl, and the others are hydrogen atoms. )

[0015]

[Chemical 6]

(In the formula, M, X ¹ and X ² are the same as those in the general formula (I), and R ^{15 to} R ¹⁹ may be the same or different, and four of them are methyl or Is ethyl and the other is hydrogen atom, or 5 is methyl or ethyl, and R ²⁰ has 1 to 10 carbon atoms.
5 is an alkyl group or a hydrogen atom. ) [II] a compound capable of activating this transition metal compound [I], and (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

The second ethylene polymer composition according to the present invention comprises (A) an ethylene polymer or ethylene and 3 carbon atoms.
A copolymer of 20 to 20 α-olefins (A-1)
The density (d _A ) is in the range of 0.96 to 0.98 g / cm ³ , and (A-2) the intrinsic viscosity [η] is 0.5 to 3.0 dl / g.
20 to 90% by weight of the ethylene polymer in the range of (B) ethylene polymer or ethylene and 3 carbon atoms
A copolymer of 20 to 20 α-olefins (B-1)
The density (d _B ) is in the range of 0.91 to 0.965 g / cm ³ , and (B-2) the intrinsic viscosity [η] is 1.0 to 10 dl / g.
In the range of 80 to 10% by weight, wherein at least one of the (A) ethylene polymer and the (B) ethylene polymer is an ethylene-based polymer produced using a metallocene catalyst. a coalescing, (1) the (a) than the the density of the ethylene polymer (d _a) (B) ratio of the density (d _B) of the ethylene-based polymer (d _a / d _B) is 1 Large (2) Density 0.940-0.970g /
in the range of cm ³ , (3) Melt flow rate (MF
R: 190 ° C., measured under 2.16 kg load) is 0.005
The melt flow rate (MFR) and the melt tension (MT) are −0.4 log (MFR) + 0.7 ≧ log (MT) ≧ −0.4 log. Satisfies the relationship shown by (MFR) + 0.1, and (5) diameter swell ratio is 1.35.
It is characterized by exceeding.

The above-mentioned ethylene polymer (A) and / or ethylene polymer (B) can be produced, for example, using the following metallocene catalyst. [I] a transition metal compound represented by the general formula (II) or a transition metal compound represented by the general formula (III), and [II] a compound capable of activating the transition metal compound [I]. And (II-1) organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The ethylene polymer composition according to the present invention will be specifically described below. First ethylene-based polymer composition The first ethylene-based polymer composition according to the present invention is formed from an ethylene-based polymer (A) and an ethylene-based polymer (B). The system polymer is produced using a metallocene catalyst.

Each of these components will be described. (A) Ethylene-based polymer The ethylene-based polymer (A) constituting the first ethylene-based polymer composition according to the present invention is an ethylene homopolymer or ethylene and an α-olefin having 3 to 20 carbon atoms. Is a random copolymer of.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and combinations thereof.

The ethylene-based polymer (A) has a unit derived from ethylene of 60 to 100% by weight, preferably 80.
To 100% by weight, more preferably 90 to 100% by weight, and 0 to 40% by weight, preferably 0 to 20% by weight, more preferably units derived from an α-olefin having 3 to 20 carbon atoms. Is desirably contained in an amount of 0 to 10% by weight.

In the present invention, the composition of the ethylene polymer is
It can be determined by ¹³ C-NMR spectrum. The ¹³ C-NMR spectrum of an ethylene polymer is usually 10
Approximately 200 mg of a sample was uniformly dissolved in 1 ml of hexachlorobutadiene in a sample tube having a measurement diameter of 120 mm.
℃, measurement frequency 25.05MHz, spectrum width 150
0Hz, pulse repetition time 4.2sec., Pulse width 6μse
It is measured under the condition of c.

(A-1) Density (d) of ethylene polymer (A)
_A ) is in the range of 0.96 to 0.98 g / cm ³ , preferably 0.965 to 0.980 g / cm ³ . In the present invention, the density of the ethylene-based polymer is 120 when the strand obtained in the melt flow rate measurement shown below is
It heat-processes at 1 degreeC for 1 hour, and after slowly cooling to room temperature over 1 hour, it measures with a density gradient tube.

(A-2) The intrinsic viscosity [η] of the ethylene polymer (A) is 0.5 to 3.0 dl / g (MFR; 1000 to
0.01 g / 10 min), preferably 0.8 to 2.0 dl /
g.

In the present invention, the intrinsic viscosity [η] of the ethylene polymer is measured in decalin at 135 ° C. In the present invention, the melt flow rate of the ethylene polymer is AST
190 ° C., 2.1 according to MD1238-65T
It is measured under a 6 kg load.

The above ethylene-based polymer (A) is
It is preferably produced using a metallocene catalyst, and particularly preferably produced using a metallocene catalyst as described below.

(B) Ethylene-Based Polymer The ethylene-based polymer (B) constituting the first ethylene-based polymer composition according to the present invention is an ethylene homopolymer or an ethylene-containing polymer having 3 to 20 carbon atoms. It is a random copolymer with α-olefin. Α- having 3 to 20 carbon atoms
Examples of the olefin include the same α-olefins as the ethylene polymer (A).

The ethylene-based polymer (B) has a unit derived from ethylene of 60 to 100% by weight, preferably 80.
-98 wt%, more preferably 90-96 wt%, 1-40 wt%, preferably 2-20 wt% units derived from α-olefins having 3-20 carbon atoms,
More preferably, it is desirable that the content is 4 to 10% by weight.

(B-1) Density (d) of ethylene polymer (B)
_B ) is from 0.91 to 0.965 g / cm ³ , preferably from 0.915 to 0.960 g / cm ³ , more preferably from 0.920 to 0.960 g / cm ³ .

(B-2) The intrinsic viscosity [η] of the ethylene polymer (B) is 1.0 to 10 (MFR; 35 to 0.0003).
g / 10 minutes) dl / g, preferably 3.0 to 10 dl / g
It is.

The ethylene-based polymer (B) as described above is
It is preferably produced using a metallocene catalyst, and particularly preferably produced using the following metallocene catalyst.

Production of ethylene-based polymer Ethylene-based polymer (A) and ethylene-based polymer (B)
At least one of the above is produced using a metallocene catalyst, but it is preferable that both the ethylene polymer (A) and the ethylene polymer (B) are produced using a metallocene catalyst.

In the present invention, as the metallocene catalyst, [I] a transition metal compound having a specific structure, [II] a compound capable of activating the transition metal compound [I], and (II-1) an organic compound Aluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. A catalyst can be used.

Each component forming such a catalyst will be described. As the transition metal compound [I], for example, a bridged metallocene compound represented by the following general formula (I) can be used.

[0036]

[Chemical 7]

In the formula, M represents a transition metal atom of Groups 4 to 6 of the periodic table, and specifically, titanium, zirconium,
Hafnium, vanadium, niobium, tantalum, chromium,
Molybdenum or tungsten, preferably titanium, zirconium or hafnium, particularly preferably zirconium.

Substituents R ^{1 to} R ⁴ R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other and have a hydrogen atom, a halogen atom or a carbon atom which may be substituted with a halogen atom. 1 to 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, and carbon atoms to which some of the groups adjacent to each other are bonded and the groups are bonded. And may form a ring together. Note that R ^{1 to} R ⁴ represented by two each indicate that when they are combined to form a ring, they are preferably combined with each other by a combination of the same symbols, for example, R ¹ and R ¹ Indicate that it is preferable to combine with and to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl , Octyl, nonyl, dodecyl,
Alkyl groups such as eicosyl, norbornyl, adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, And aryl groups such as biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

Further, these hydrocarbon groups may be substituted with halogen. The ring formed by combining R ^{1 to} R ⁴ includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Fused rings such as indene rings, benzene rings, naphthalene rings,
Examples include an alkyl group such as methyl, ethyl, propyl, and butyl, and a group in which a hydrogen atom on a condensed ring group such as an acenaphthene ring and an indene ring is substituted with halogen.

Examples of the silicon-containing group include monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. , Trihydrocarbyl-substituted silyl such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether; silicon-substituted alkyl group such as trimethylsilylmethyl; silicon such as trimethylphenyl. Examples thereof include a substituted aryl group.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. Can be mentioned.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate group, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate and other sulfonate groups, methylsulfinate, phenylsulfinate, benzenesulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

As the nitrogen-containing group, an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino. And an arylamino group or an alkylarylamino group.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino. X ¹ and X ² X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, an oxygen-containing group. , A sulfur-containing group or a nitrogen-containing group. Specific examples of these atoms or groups include the same atoms and groups as those described for R ^{1 to} R ⁴ .

Y Y is a divalent hydrocarbon group, a divalent silicon-containing group or 2
It is a valent germanium-containing group.

Specifically, as the divalent hydrocarbon group,
Methylene, dimethyl methylene, 1,2-ethylene, dimethyl
-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and other alkylene groups; diphenylmethylene, diphenyl-1,2
-Aryl alkylene groups such as ethylene.

Examples of the divalent silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, Alkylsilylene such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyldisilyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl , Alkylaryldisilyl, aryldisilyl groups and the like.

Examples of the divalent germanium-containing group include compounds in which silicon in the divalent silicon-containing group is replaced with germanium. Such a transition metal compound [I]
Examples thereof include dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis ( Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene- (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene-bis (1
-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, ethylene- (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride and the like can be mentioned.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds. In addition, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be mentioned.

Among the transition metal compounds represented by the general formula (I), transition metal compounds represented by the following general formula (Ia) are preferably used.

[0052]

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(In the formula, M, R ¹ , R ³ , X ¹ , X ² and Y are the same as those in formula (I), and R ^{21 to} R ²⁴ and R ⁴¹
To R ⁴⁴ represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and the alkyl group or the aryl group may be substituted with a halogen or an organic silyl group. ) More specifically, examples of the compound represented by the formula (Ia) include dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dibromide, and dimethylsilylene-bis (indenyl) dimethyl. Zirconium, dimethylsilylene-bis (indenyl) diphenylzirconium, dimethylsilylene-bis (indenyl) methylzirconium monochloride, dimethylsilylene-bis (indenyl) zirconium bis (methanesulfonate), dimethylsilylene-bis (indenyl) zirconium bis ( p
-Toluenesulfonate), dimethylsilylene-bis (indenyl) zirconiumbis (p-toluenesulfonate), dimethylsilylene-bis (indenyl) zirconiumbis (trifluoromethanesulfonate),
Dimethylsilylene-bis (indenyl) zirconium trifluoromethanesulfonate, dimethylsilylene-
Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene-bis (2-methylindenyl) zirconium dichloride, dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethyl Silylene- (indenyl) (fluorenyl) zirconium dichloride, dimethylsilylene-
Bis (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl)
Dimethyl zirconium, ethylene-bis (indenyl)
Zirconium dichloride, ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene-bis (indenyl) zirconium bis (p-toluenesulfonate) , Ethylene-bis (indenyl) zirconium bis (p-chlorobenzenesulfonate), ethylene-bis (2-methylindenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (2-methyl Indenyl)
Zirconium dichloride, dimethylsilylene-bis (4,5
-Benzoindenyl) zirconium dichloride, dimethylsilylene-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene- (2-methyl-
4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, methylene-bis (2- Methyl-4-phenylindenyl)
Zirconium dichloride, ethylene-bis (2-methyl-4-
Phenylindenyl) zirconium dichloride, dimethylsilylene-bis (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene-bis (2-ethyl-4- (α-naphthyl) indenyl) zirconium dichloride, ethylene-bis ( 2-ethyl-4-phenylindenyl) zirconium dichloride, ethylene-bis (2-ethyl
-4- (α-naphthyl) indenyl) zirconium dichloride, ethylene-bis (2-n-propyl-4- (α-naphthyl) indenyl) zirconium dichloride, ethylene-bis (2,4,7-trimethylindenyl) zirconium Dichloride, isopropylidene-bis (2,4,7-trimethylindenyl) zirconium dichloride and the like.

In the present invention, as the transition metal compound [I], a non-crosslinked metallocene compound represented by the following general formula (II) or (III) can also be used.

[0055]

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In the formula, M, X ¹ and X ² are the same as in the general formula (I). R ^{5 to} R ⁹ may be the same or different, and at least two of them are methyl or ethyl, and the others are hydrogen atoms.

R ^{10 to} R ¹⁴ may be the same or different from each other, and at least two of them are methyl or ethyl, and the others are hydrogen atoms. Specific examples of the compound represented by the general formula (II) include bis (1,3-
Dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1,2,3-
Trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl)
Zirconium dichloride, (1,3-dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride and the like can be mentioned.

[0058]

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In the formula, M, X ¹ and X ² are the same as in the general formula (I). R ¹⁵ to R ¹⁹ may be the same or different from each other, is four methyl or ethyl of which, and the other is hydrogen atom, or 5 is methyl or ethyl.

R ²⁰ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl and the like.

Specific examples of the compound represented by the general formula (III) include (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (pentaethylcyclopentadienyl) (cyclopentapentyl). (Dienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (butylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (1,3-Dimethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl)
(1-butyl-3-methylcyclopentadienyl) zirconium dichloride and the like.

Of these, those having a 5-substituted cyclopentadienyl ring and an unsubstituted cyclopentadienyl ring are particularly preferable. Compound [II] capable of activating the above transition metal compound [I] (hereinafter also referred to as “component [II]”)
(II-1) organoaluminum compound, (II-2)
Aluminoxane and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair are used.

The organoaluminum compound (II-1) (hereinafter also referred to as "component (II-1)") is represented by, for example, the following general formula (i). During ^{_{R a n AlX 3-n ...}} (i) ( wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
It is 3. ) In formula (i), R ^a is the number of carbon atoms 1 to 1
A hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, Octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Such an organoaluminum compound (II-
1) is, specifically, trimethylaluminum,
Triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, trialkylaluminum such as tri-2-ethylhexylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, Dialkylaluminum halides such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, alkylaluminum sesquichlorides such as ethylaluminum sesquibromide, methylaluminum dichloride Ethylaluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide,
Examples thereof include alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, as the organoaluminum compound (II-1), a compound represented by the following general formula (ii) can also be used. R ^a _n AlY _3-n (ii) (where R ^a is the same as described above, Y is an —OR ^b group,
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
a iR ^f ₃ group or -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., wherein ^Re is a hydrogen atom,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like. Specific examples include the following compounds. (1) Compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (2) R ^a _n Al (OSiR ^c ₃ ) _{3 -n} , for example, Et ₂ Al (OSiMe ₃ ), (iso-
(Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
SiEt ₃₎ such _{^{as, (3) R a n Al}} (OAlR d 2) 3-n
For example, Et ₂ AlOAAlE
t ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc.
_{^{(4) R a n Al (}} NR e 2) a compound represented by _{3-n, e.g., Me 2 AlNEt 2, Et 2} AlNHMe, M
e ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (i
so-Bu) ₂ AlN (such as _{SiMe 3) 2, (5)} R a n
A compound represented by Al (SiR ^f ₃ ) _3-n , for example,
(6) R ^a _n Al such as (iso-Bu) ₂ AlSi Me ₃
^{(N (R g) AlR h} 2) a compound represented by _{3-n, e.g., Et 2 AlN (Me) AlEt} 2, (iso-Bu) 2
AlN (Et) Al (iso-Bu) ₂ etc.

Of these, the general formulas R ^a ₃ Al, R ^{a
_{n Al (OR b) 3-}} n, R a n Al (OAlR d 2) 3-n
The compound represented by is particularly preferable, and a compound in which ^Ra is an isoalkyl group and n = 2 is particularly preferable.

The organoaluminum compound (II-1) can be used in combination. Aluminoxane (II-2)
(Hereinafter, also referred to as “component (II-2)”) may be a conventionally known benzene-soluble aluminoxane, or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807. May be

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, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a suspension of a hydrocarbon medium such as aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, and the adsorbed water or water of crystallization is added to the suspension. A method of reacting with an aluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

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

Specific examples of the organoaluminum compound used for producing the aluminoxane include the same ones as those shown above as the organoaluminum compound (II-1).

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable. The organoaluminum compounds can also be used in combination.

Solvents used in the production of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated compounds And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound has an Al component dissolved in benzene at 60 ° C. of 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom. Insoluble or sparingly soluble.

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%).

A compound (II-3) which reacts with the transition metal compound [I] to form an ion pair (hereinafter referred to as "component (II-3)").
JP-A-1-501950,
JP-A-1-502036, JP-A-3-17900
No. 5, JP-A-3-179006, JP-A-3-179006
207703, JP-A-3-207704,
Lewis acids described in USP-5321106 and the like,
Ionic compounds and carborane compounds can be mentioned.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ -A
l ₂ O _{3 and the} like.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferroferrite. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carborane compound include dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate and tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be mentioned.

The component (II-3) can be used in combination of two or more kinds. As the compound [II] capable of activating the transition metal compound [I], the above-mentioned component (II-1), component (II-2) or component (II-3) can be used in combination.

[III] The carrier has a particle size of 10 to 300.
μm, preferably 20 to 200 μm
Particulate solids are used. As this carrier, there is no porous material.
Organic oxides are preferably used, specifically, SiO 2 ₂, A
l₂O_Three, MgO, ZrO₂, TiO₂, B₂O_Three, Ca
O, ZnO, BaO, ThO₂Etc or a mixture of these
Object, eg SiO₂-MgO, SiO₂-Al ₂O_Three, Si
O₂-TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three,
SiO₂-TiO₂-MgO or the like is used. Among these
Then, SiO₂And / or Al ₂O_ThreeIs the main component
Are preferred.

A small amount of Na is contained in the above inorganic oxide.₂CO
_Three, K₂CO_Three, CaCO_Three, MgCO_Three, Na₂S
O_Four, Al₂(SO_Four)_Three, BaSO_Four, KNO_Three, Mg
(NO_Three) ₂, Al (NO_Three)_Three, Na₂O, K₂O, Li
₂Contains carbonate, sulfate, nitrate and oxide components such as O
It may be.

The carrier [III] has a specific surface area of 50 to 1000 m, although its properties vary depending on the type and production method.
² / g, more preferably 100 to 700 m ² / g, and those having a pore volume of 0.3 to 2.5 cm ³ / g are preferably used.

If necessary, such an inorganic carrier may be used.
It can be used after firing at 0 to 1000 ° C, preferably 150 to 700 ° C. The amount of water adsorbed on the carrier [III] is
It is preferably less than 1.0% by weight, more preferably 0.1% by weight.
More preferably, it is less than 5% by weight. Further, the surface hydroxyl group is preferably at least 1.0% by weight, more preferably 1.5 to 4.0% by weight, and particularly preferably 2.0 to 3.5% by weight.

Here, the amount of adsorbed water (% by weight) of the carrier is 2
The weight loss when dried at a temperature of 00 ° C. for 4 hours under a normal pressure and a nitrogen flow is determined as the amount of adsorbed water. The amount of surface hydroxyl groups (% by weight) of the carrier is 200 ° C. at normal pressure,
The weight of the carrier obtained by drying under nitrogen flow for 4 hours is X
(G), and the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours and having no surface hydroxyl groups obtained is represented by Y
(G) can be calculated by the following equation.

Surface hydroxyl group amount (% by weight) = {(X−Y) / X} × 100 Further, an organic compound can be used as the carrier [III], for example, ethylene, propylene, 1-butene, 4-methyl. -1-Use of a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer or copolymer produced mainly from vinylcyclohexane or styrene. You can

The catalyst preferably used for producing the ethylene-based polymer (A) and the ethylene-based polymer (B) has the above-mentioned carrier [III] and the transition metal compound [I] and the component [II]. It is a carrier-supported metallocene catalyst (solid catalyst) that is supported.

This solid catalyst is composed of component [I] and component [II].
And the carrier [III] can be prepared by bringing the component [II] into contact with the carrier [III] in any order.
And then mixed contact with the transition metal compound [I].

Each of these components can be contacted in an inert hydrocarbon solvent. Examples of the solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and hexadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and cyclooctane;
Aromatic hydrocarbons such as benzene, toluene and xylene,
Halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, petroleum fractions such as gasoline, kerosene and light oil, and mixtures thereof can be used.

In preparing a catalyst from each of these components, the transition metal compound [I] is usually used in an amount of 5 × 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 per 1 g of the carrier [III].
× 10 ^- used ⁴ molar quantities. The component [II] is an atomic ratio (Al or B / transition metal) of aluminum or boron of the component [II] to the transition metal of the transition metal compound [I], and is usually 10 to 500, preferably 20 to 200. Used in. When the organoaluminum compound (II-1) and the aluminoxane (II-2) are used as the component [II], the aluminum atom (Al-
The atomic ratio (Al-1 / Al-2) between 1) and the aluminum atom (Al-2) in the component (II-2) is 0.02 to 3, and more preferably 0.0.
It is preferably used in an amount of 5 to 1.5.

Each of these components is usually -50 to 150 ° C,
Preferably at a temperature of -20 to 120 ° C for 1 minute to 50 hours,
The contact is preferably performed for 10 minutes to 25 hours. In the solid catalyst prepared as described above, the transition metal compound [I] as the transition metal atom is 5 × 10 ⁻⁶ to 1 g of the carrier [III].
It is preferably carried in an amount of 5 × 10 ⁻⁴ gram atoms, and more preferably in an amount of 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atoms. The component [II] is
It is desirable that the carrier [III] is supported in an amount of 10 ^{−3 to} 5 × 10 ⁻² g atom as aluminum atom or boron atom per 1 g, and further 2 × 10 ⁻³ to 2 × 10.
It is preferably carried in an amount of ^-2 gram atoms.

For the (co) polymerization of ethylene, the solid catalyst as described above can be used as it is, but it is also possible to preliminarily polymerize an olefin on the solid catalyst to form a prepolymerized catalyst before use.

The prepolymerization catalyst is composed of the above components [I] to [II].
In the presence of [I], it can be usually prepared by prepolymerizing an olefin in an inert hydrocarbon solvent.
Preferably, a solid catalyst is formed from each of the components [I] to [III]. In addition to this solid catalyst, component [II] may be further added.

During the prepolymerization, the transition metal compound [I]
Is usually 5 × 10 ^{−6 to} 5 × 10 ⁶ per 1 g of the carrier [III].
^-4 mol, preferably used in an amount of 10 ^-5 to 2 × 10 ^-4 mol. The component [II] is an atomic ratio of aluminum or boron in the component [II] to the transition metal in the transition metal compound [I] (Al or B / transition metal) and is usually 10 to 5%.
00, preferably from 20 to 200. When the organoaluminum compound (II-1) and the aluminoxane (II-2) are used as the component [II], the aluminum atom (Al-1) in (II-1) and the aluminum atom in (II-2) The atomic ratio (Al-1 / Al-2) of (Al-2) is 0.0
It is preferably used in an amount of 2 to 3, more preferably 0.05 to 1.5.

The concentration of the transition metal compound [I] or the solid catalyst formed from each component in the prepolymerization system is usually 10 ⁻⁶ to 2 × 10 ^{−2 in} terms of the transition metal / polymerization volume of 1 liter.
Mol / l, more preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / l.

The prepolymerization is usually carried out at a temperature of -20 to 60 ° C, preferably 0 to 50 ° C for 0.5 to 100 hours, preferably 1 to 50 hours. As the prepolymerized olefin, ethylene and an α-olefin having 3 to 20 carbon atoms as described above can be used, and these may be copolymerized.

The prepolymerization catalyst may be prepared by using an inert hydrocarbon solvent to introduce the olefin into a solid catalyst suspension, or the solid catalyst produced in the inert hydrocarbon solvent may be added to the suspension. After separation, it may be suspended again in an inert hydrocarbon, and the olefin may be introduced into the resulting suspension. Specifically, for example, it can be prepared as follows.

The carrier [III] is suspended in an inert hydrocarbon, and the component [II] (eg (II-2)) is added to this suspension and reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. The transition metal compound [I] is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst.

Next, an organoaluminum compound (component (II
-1)) to the inert hydrocarbon containing the solid catalyst obtained above, and by introducing an olefin therein and polymerizing, a prepolymerized catalyst is obtained.

Prepolymerization produces an olefin polymer (prepolymer) in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g, per 1 g of the carrier [III]. Is desirable.

In the thus obtained prepolymerized catalyst, the transition metal compound [I] per 1 g of the carrier [III] as a transition metal is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ^−5. in an amount of to 2 × 10 ^-4 gram atom, the component [I
I] is the molar ratio of aluminum or boron in component [II] to transition metal (Al or B / transition metal), 5
It is desirable that the catalyst is carried in an amount of from 200 to 200, and more preferably from 10 to 150.

Preliminary polymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or increased pressure. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of 0.2 to 7 dl / g, preferably 0.1 μm, in the presence of hydrogen.
It is desirable to produce a prepolymer of about 5 to 5 dl / g.

In the production of the ethylene-based polymer (A) and the ethylene-based polymer (B), ethylene is polymerized in the presence of the above solid catalyst or prepolymerization catalyst, or ethylene and other α-olefins are used. And are copolymerized.

This (main) polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, or gas phase polymerization methods. Further, it can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used, and specifically, the same solvent as that shown at the time of preparing the catalyst can also be used. In the (main) polymerization, the solid catalyst or the pre-polymerization catalyst is transition metal / liter (polymerization volume), usually 10 ^-8 to 10 ^-3 gram atom / liter,
More preferably, it is used in an amount of 10 ^-7 to 10 ^-4 gram atom / liter.

Further, the component [II] may be added to the main polymerization carried out using the prepolymerization catalyst. Ingredient [II] is
Atomic ratio of aluminum or boron in component [II] to transition metal during main polymerization (Al or B / transition metal)
5 to 300, preferably 10 to 200, and more preferably 15 to 150.

The (main) polymerization is usually carried out at a temperature of from -50 to 200 ° C, preferably from 0 to 100 ° C, and usually from atmospheric pressure to 10.
It can be carried out under a pressure of 0 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² . It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

Particularly when the ethylene polymer (A) and the ethylene polymer (B) are produced by suspension polymerization,
It is desirable to carry out each at a polymerization temperature of 0 to 200 ° C., preferably 20 to 150 ° C.
It is desirable to carry out at a polymerization temperature of ˜120 ° C., preferably 60 to 110 ° C.

The molecular weight of the resulting ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. Ethylene-based polymer composition The first ethylene-based polymer composition according to the present invention comprises the ethylene-based polymer (A) and the ethylene-based polymer (B) as described above, and the ethylene-based polymer ( A) 20 to 9
Ethylene polymer (B) in an amount of 0% by weight, preferably 30 to 80% by weight, more preferably 40 to 75% by weight.
In an amount of 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 25 to 60% by weight.

Further, this ethylene polymer composition is
Wherein (A) and the density of the ethylene-based polymer (d _A) (B) ratio of the density (d _B) of the ethylene-based polymer (d _A / d _B) is 1
It is formed from the ethylene-based polymer (A) and the ethylene-based polymer (B) having a larger size, preferably 1 to 1.2, and more preferably 1.005 to 1.08.

The first ethylene polymer composition according to the present invention satisfies the following characteristics (1) to (4). (1) The density is in the range of 0.940 to 0.970 g / cm ³ , preferably 0.945 to 0.970 g / cm ³ , more preferably 0.950 to 0.965 g / cm ³ .

(2) The melt flow rate (MFR) is
0.005 to 20 g / 10 minutes, preferably 0.008 to 8
g / 10 minutes, more preferably 0.01 to 1.5 g / 10 minutes.

(3) The melt tension (MT) value and the melt flow rate (MFR) value of the ethylene polymer composition according to the present invention are represented by the following formula log (MT) ≥ -0.4 log (MFR). It satisfies +0.70.

The melt flow rate (MFR) value and the melt tension (MT) value of the ethylene polymer composition satisfying such a relational expression are specifically 1 to 100 g, more preferably 2 to 50 g. Is desirable.

Melt tension (MT) is measured as stress when a molten sample is stretched at a constant rate. In the present invention, specifically, a molten sample (ethylene-based polymer composition) was measured using an MT measuring machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, and a winding speed of 1 mm.
It is measured as a stress when stretched under the conditions of 0 to 20 m / min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm.

(4) The diameter swell ratio exceeds 1.35, preferably 1.35 to 1.65. The ethylene polymer composition having such a diameter swell ratio is excellent in moldability. For example, when this ethylene-based polymer composition is blow-molded, a bottle having excellent strength can be obtained because of good pinch-off shape. Further, since the wall thickness distribution of the bottle (hollow molded body) can be narrowed, the basis weight can be reduced, and if the basis weight is the same, a bottle excellent in buckling strength can be obtained.

The swell ratio of the ethylene polymer composition can be measured as follows. Capirograph-1B (manufactured by Toyo Seiki Seisakusho, barrel diameter 10 mm)
Tubular nozzle (inner diameter (D ₀ ) 3mm, outer diameter 4m
m, length 10 mm) is attached, and the barrel (portion where sample is put) is heated to 200 ° C. and held. Approximately 1 sample in barrel
After adding 0 g, mounting a piston, removing air bubbles, preheating for 6 minutes. After preheating 10, 20, 30, 5
The sample was extruded at each piston speed of 0, 75 (mm / min), and the strand diameter (D
_i ) is measured with a laser beam.

The ratio (SR _i = D _i / D ₀ ) of the strand diameter (D _i ) at each piston speed and the tube nozzle diameter (D ₀ ) measured in this way is shown on a semilogarithmic graph paper. The SR value when the piston speed is 50 (mm / min) is read from the curve obtained by plotting for each piston speed, and this SR value is taken as the diameter swell ratio. It should be noted that it is also possible to obtain the shear speed corresponding to the piston speed.

The first ethylene-based polymer composition according to the present invention is a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent as long as the object of the present invention is not impaired. , Various additives such as anti-fog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be contained.

Second Ethylene Polymer Composition Next, the second ethylene polymer composition according to the present invention will be described. The second ethylene-based polymer composition according to the present invention is formed from the ethylene-based polymer (A) and the ethylene-based polymer (B), and at least one of the ethylene-based polymers uses a metallocene catalyst. It is manufactured.

(A) Ethylene Polymer and (B) Ethi
Ren-based polymer Ethylene-based polymer (A) and ethylene-based polymer (B) constituting the second ethylene-based polymer composition according to the present invention
Examples thereof include the same ones as the ethylene polymer (A) and the ethylene polymer (B) that form the first ethylene polymer composition.

Production of ethylene-based polymer Ethylene-based polymer (A) and ethylene-based polymer (B)
At least one of the above is produced using a metallocene catalyst, but it is preferable that both the ethylene polymer (A) and the ethylene polymer (B) are produced using a metallocene catalyst.

In the present invention, as the metallocene catalyst, [I] the transition metal compound represented by the general formula (II) or the transition metal compound represented by the general formula (III), and [II] the transition metal compound A compound capable of activating the compound [I], and (II-1) an organoaluminum compound, (II-
A carrier-supported metallocene composed of 2) an aluminoxane, and (II-3) at least one compound selected from the compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. A catalyst can be used.

Examples of the compound [II] and [III] carriers capable of activating the above transition metal compound [I] include the same carriers as described above. The method for preparing a solid catalyst and a prepolymerized catalyst using such a catalyst component is the same as described above.

In the production of the ethylene-based polymer (A) and the ethylene-based polymer (B), ethylene is polymerized in the presence of the solid catalyst or the prepolymerization catalyst as described above, or ethylene and another α-olefin are used. And are copolymerized.

This (main) polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, or gas phase polymerization methods. Further, it can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used, and specifically, the same solvent as that shown at the time of preparing the catalyst can also be used. In the (main) polymerization, the solid catalyst or the pre-polymerization catalyst is transition metal / liter (polymerization volume), usually 10 ^-8 to 10 ^-3 gram atom / liter,
More preferably, it is used in an amount of 10 ^-7 to 10 ^-4 gram atom / liter.

The component [II] may be added to the main polymerization carried out using the prepolymerization catalyst. Ingredient [II] is
Atomic ratio of aluminum or boron in component [II] to transition metal during main polymerization (Al or B / transition metal)
5 to 300, preferably 10 to 200, and more preferably 15 to 150.

The (main) polymerization is usually carried out at a temperature of from -50 to 200 ° C, preferably from 0 to 100 ° C, and usually from atmospheric pressure to 10 ° C.
It can be carried out under a pressure of 0 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² . It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

Especially when the ethylene polymer (A) and the ethylene polymer (B) are produced by suspension polymerization,
It is desirable to carry out each at a polymerization temperature of 0 to 200 ° C., preferably 20 to 150 ° C.
It is desirable to carry out at a polymerization temperature of ˜120 ° C., preferably 60 to 110 ° C.

The molecular weight of the obtained ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. Ethylene-based polymer composition The second ethylene-based polymer composition according to the present invention comprises the ethylene-based polymer (A) and the ethylene-based polymer (B) as described above, and the ethylene-based polymer ( A) 20 to 9
Ethylene polymer (B) in an amount of 0% by weight, preferably 30 to 80% by weight, more preferably 40 to 75% by weight.
In an amount of 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 25 to 60% by weight.

Further, this ethylene polymer composition is
Wherein (A) and the density of the ethylene-based polymer (d _A) (B) ratio of the density (d _B) of the ethylene-based polymer (d _A / d _B) is 1
It is formed from the ethylene-based polymer (A) and the ethylene-based polymer (B) having a larger size, preferably 1 to 1.2, and more preferably 1.005 to 1.08.

The second ethylene polymer composition according to the present invention satisfies the following characteristics (1) to (4). (1) The density is in the range of 0.940 to 0.970 g / cm ³ , preferably 0.945 to 0.970 g / cm ³ , more preferably 0.950 to 0.965 g / cm ³ .

(2) The melt flow rate (MFR) is
0.005 to 20 g / 10 minutes, preferably 0.008 to 8
g / 10 minutes, more preferably 0.01 to 5.0 g / 10 minutes.

(3) The melt tension (MT) value and the melt flow rate (MFR) value of the ethylene polymer composition according to the present invention are represented by the following formula: −0.4 log (MFR) + 0.7 ≧ log (MT) ≧ −0.4 log (MFR) +0.1 is satisfied.

(4) The diameter swell ratio exceeds 1.35, preferably 1.35 to 1.65. The ethylene polymer composition having such a diameter swell ratio is excellent in moldability.

The second ethylene polymer composition according to the present invention may contain the same various compounding ingredients as described above, as long as the object of the present invention is not impaired. Method for Producing Ethylene-Based Polymer Composition The first and second ethylene-based polymer compositions according to the present invention have the above-mentioned ethylene-based polymer (A) and ethylene-based polymer (B) prepared by a known method. Blend or
Alternatively, it can be directly produced by polymerization.

As the blending method, (1) a method of blending the ethylene-based polymer (A), the ethylene-based polymer (B) and, if desired, other components with an extruder, a kneader or the like, (2) an ethylene-based polymer The polymer (A), the ethylene-based polymer (B) and, if desired, other components are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, xylene), Then, a method of removing the solvent, (3) preparing a solution in which the ethylene polymer (A), the ethylene polymer (B) and optionally other components are separately dissolved in a suitable good solvent, and then mixed, Then, a method of removing the solvent, (4) a method of combining the above methods (1) to (3), and the like can be mentioned.

As a method for directly producing an ethylene-based polymer composition comprising the ethylene-based polymer (A) and the ethylene-based polymer (B) by polymerization, for example, the above-mentioned polymerization may be carried out under different reaction conditions. A method of producing an ethylene-based polymer composition by producing the ethylene-based polymer (A) and the ethylene-based polymer (B) by performing the steps in more than one step.

The first and second ethylene polymer compositions according to the present invention are excellent in moldability and can be subjected to various methods such as blow molding, vacuum / pressure molding, inflation molding, extrusion molding and foam molding. Thus, it can be used for a wide range of applications, for example, by forming it into a drug can, a drum, a bottle, an inflation film, a pipe and the like. Also, molded articles formed in this way, such as engineering cans, drums,
Bottles have excellent rigidity and mechanical strength.

[0140]

EFFECT OF THE INVENTION The ethylene polymer composition according to the present invention is excellent in moldability and can produce a molded product excellent in mechanical strength such as stress crack resistance and rigidity.

[0141]

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

In the present invention, the physical properties of the ethylene polymer composition were evaluated as follows. [Izod impact strength (IZ)] A test was performed according to JIS K7110. The test temperature was -30 ° C.

[ESCR Measurement] ASTM D1693
It was carried out according to. Measurement conditions (temperature: 50 ° C., surfactant: Antalox CO-630, surfactant concentration: 10%)

[0144]

[Synthesis Example 1] [Preparation of solid catalyst (a)] 5.0 g of silica dried at 250 ° C for 10 hours was suspended in 80 ml of toluene, and then cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al; 1.33 mol / L) 2
8.7 ml 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 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 in 80 ml of toluene.
100 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr; 0.00192 mmol / ml) was added to this system at room temperature, and the mixture was further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed three times with hexane to obtain a solid catalyst (a) containing 2.4 mg of zirconium per gram.

[Preparation of Preliminary Polymerization Catalyst (A)] 7 g of the solid catalyst (a) obtained above was resuspended in 200 ml of hexane. To this system, 9.5 ml of a decane solution of triisobutylaluminum (1 mmol / ml) was added, and ethylene was prepolymerized at 35 ° C. for 2 hours to prepare a solid catalyst 1.
A prepolymerized catalyst (A) containing 2.2 mg of zirconium per g and preliminarily polymerized with 3 g of an ethylene polymer was obtained.

[0147]

[Synthesis Example 2] [Preparation of solid catalyst (b)] In Synthesis Example 1, instead of a toluene solution of ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was prepared. 86m of a toluene solution (Zr; 0.00223 mmol / ml)
A solid catalyst (b) was obtained in the same manner as in Synthesis Example 1 except that 1 was used.

[Preparation of Prepolymerized Catalyst (B)] The prepolymerized catalyst (A) was prepared in the same manner as the prepolymerized catalyst (A) except that the solid catalyst (b) was used instead of the solid catalyst (a) and the prepolymerized catalyst was used for 1.5 hours. In the same manner as in the preparation, a prepolymerized catalyst (B) containing 2.0 mg of zirconium per 1 g of the solid catalyst and preliminarily polymerized with 3 g of an ethylene polymer was obtained.

[0149]

[Synthesis Example 3] [Preparation of solid catalyst (c)] Instead of the toluene solution of ethylenebis (indenyl) zirconium dichloride in Synthesis Example 1, a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was used. (Zr;
A solid catalyst (c) was obtained in the same manner as in Synthesis Example 1 except that 24 ml of 0.00778 mmol / ml) was used.

[Preparation of prepolymerized catalyst (C)] [0150] The same procedure as in preparation of the prepolymerized catalyst (A) was used except that the solid catalyst (c) was used in place of the solid catalyst (a). A prepolymerized catalyst (C) containing 2.3 mg of zirconium and preliminarily polymerized with 3 g of an ethylene polymer was obtained.

[0151]

[Synthesis Example 4] [Preparation of solid catalyst (d)] In Synthesis Example 1, instead of a toluene solution of ethylenebis (indenyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride was prepared. A solid catalyst (d) was obtained in the same manner as in Synthesis Example 1 except that 22 ml of a toluene solution (Zr; 0.00851 mmol / ml) was used.

[Preparation of Preliminary Polymerization Catalyst (D)] In the same manner as in the preparation of prepolymerization catalyst (A) except that the solid catalyst (d) was used in place of the solid catalyst (a), per 1 g of solid catalyst A prepolymerized catalyst (D) containing 2.3 mg of zirconium and preliminarily polymerized with 3 g of an ethylene polymer was obtained.

[0153]

[Production Example 1] Production of ethylene-based polymer (1) 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and the inside of the system was adjusted to 7
It was brought to 0 ° C. and replaced with ethylene. Next, 1.5 ml of a decane solution of triisobutylaluminum (1 mmol / ml) and 0.01 mmol of the prepolymerization catalyst (A) in terms of zirconium atom were added to the autoclave.

1500 Nml hydrogen in the autoclave
Was added and ethylene was further introduced, and the total pressure was 8 kg / cm.
Polymerization was initiated as ^2- G. The temperature in the system immediately rose to 80 ° C.

Then, only ethylene was replenished to bring the total pressure to 8
Polymerization was carried out at 80 ° C. for 1.5 hours while maintaining the pressure at kg / cm ² -G. After the polymerization was completed, the polymer was filtered and then dried at 80 ° C. overnight. 284 g of ethylene polymer (1) (homopolyethylene) was obtained.

The density of this ethylene polymer (1) was 0.
It was 972 g / cm ³ , [η] was 1.3 dl / g, and MFR was 18.5 g / 10 minutes.

[0157]

Production Example 2 Production of Ethylene Polymer (2) Ethylene was polymerized in the same manner as in Production Example 1 except that 1000 Nml of hydrogen was added. 446 g of ethylene polymer (2) (homopolyethylene) was obtained.

The density of this ethylene polymer (2) was 0.
It was 964 g / cm ³ , [η] was 1.71 dl / g, and MFR was 1.90 g / 10 min.

[0159]

[Production Example 3] Production of ethylene polymer (3) In the same manner as in Production Example 1 except that hydrogenation was not carried out,
Ethylene was polymerized. 572 g of ethylene polymer (3) (homopolyethylene) was obtained.

The density of this ethylene-based polymer was 0.951.
g / cm ³ , [η] is 4.0 dl / g, M
FR was 0.002 g / 10 minutes.

[0161]

[Production Example 4] Production of ethylene-based polymer (4) 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, and the system was heated to 70 ° C and replaced with ethylene.

Then, 40 ml of 1-hexene and a decane solution of triisobutylaluminum (1 mmol / ml)
1.5 ml and 0.0025 mmol of the prepolymerized catalyst (A) in terms of zirconium atom were added to the autoclave. Ethylene was introduced into the autoclave and the total pressure was 8 kg / cm ² -G to start the polymerization. The temperature in the system immediately rose to 80 ° C.

After that, ethylene was replenished to bring the total pressure to 8 kg.
/ Cm ² -G, and polymerization was carried out at 80 ° C. for 1.5 hours.
After the polymerization was completed, the polymer was filtered and then dried at 80 ° C. overnight. 437 g of ethylene polymer (4) (ethylene
A hexene copolymer) was obtained.

This ethylene polymer (4) contained 3.0 mol% of units derived from 1-hexene. The ethylene polymer has a density of 0.925 g / cm ³ , [η] of 3.2 dl / g, and an MFR of 0.01.
g / 10 minutes.

[0165]

[Production Example 5] Production of ethylene-based polymer (5) Ethylene was polymerized in the same manner as in Production Example 4 except that 5 ml of 1-hexene was added and 500 N-ml of hydrogen was added. 212 g of ethylene polymer (5) (ethylene / hexene copolymer) was obtained.

The density of this ethylene polymer is 0.95.
6 g / cm ³ , [η] is 1.8 dl / g,
The MFR was 1.0 g / 10 minutes.

[0167]

Production Example 6 Production of Ethylene Polymer (6) Ethylene was polymerized in the same manner as in Production Example 4 except that 10 ml of 1-hexene was added. 332 g of ethylene polymer (6) (ethylene / hexene copolymer) was obtained.

The density of this ethylene-based polymer was 0.938.
g / cm ³ , [η] is 3.0 dl / g, and M
FR was 0.01 g / 10 minutes.

[0169]

Example 1 Production of Ethylene Polymer Composition (1) 35 g of ethylene polymer (1) obtained in Production Example 1, 15 g of ethylene polymer (3) obtained in Production Example 3 and phenol system Heat-resistant stabilizer (Irganox 1076, manufactured by Ciba-Geigy Co., Ltd.) 0.05 g, phosphorus heat-resistant stabilizer (Irgafos 168)
Ciba-Geigy Co., Ltd.) 0.025 g was dry blended and then melt-kneaded at 200 ° C. using a batch kneader (Laboplast Mill, Toyo Seiki Co., Ltd.).

The ethylene polymer composition (1) thus obtained had a density of 0.966 g / cm ³ and an MFR of 2.2 g / cm ^3.
It was 10 minutes. The results are shown in Table 1.

[0171]

Example 2 Production of Ethylene Polymer Composition (2) In Example 1, the ethylene polymer (2) was used in place of the ethylene polymer (1), and the ethylene polymer (3) was used.
An ethylene polymer composition (2) was obtained in the same manner as in Example 1 except that the ethylene polymer (4) was used instead.

The ethylene polymer composition (2) obtained had a density of 0.951 g / cm ³ and an MFR of 0.61 g.
/ 10 minutes. The results are shown in Table 1.

[0173]

Example 3 Production of Ethylene Polymer Composition (3) 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, and the system was heated to 70 ° C. and replaced with ethylene. . Then, a solution of triisobutylaluminum in decane (1 mmol / ml)
1.5 ml and 0.005 mmol of the prepolymerized catalyst (B) in terms of zirconium atom were added to the autoclave. Furthermore, ethylene is introduced into the autoclave,
Polymerization was started at a total pressure of 8 kg / cm ² -G. The temperature in the system immediately rose to 80 ° C. Thereafter, only ethylene was supplied, and the polymerization was carried out at 80 ° C. for 0.5 hour while maintaining the total pressure at 8 kg / cm ² -G (step (i)).

After completion of the polymerization, the supply of ethylene was stopped, and a mixed gas of ethylene and hydrogen (hydrogen content; 0.7 mol%) was introduced instead, and further polymerization was carried out at 80 ° C. for 1 hour (step (ii )).

After the polymerization was completed, the polymer was filtered and
Dry overnight at ° C. 264 g of ethylene polymer composition (3) was obtained. 50 g of the obtained ethylene-based polymer composition (3) and a phenolic heat stabilizer (Irganox
1076, Ciba-Geigy Co., Ltd.) 0.05 g, phosphorus-based heat stabilizer (Irgafos 168, Ciba-Geigy Co., Ltd.) 0.02
After dry blending 5 g, a batch type kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.) was used and melt-kneaded at 200 ° C.

The ethylene polymer composition (3) obtained had a density of 0.958 g / cm ³ and an MFR of 0.02 g.
/ 10 minutes (intrinsic viscosity [η]; 3.57 dl / g). As a result of performing only the step (i), 106 g of an ethylene polymer having a density of 0.941 g / cm ³ and an intrinsic viscosity [η] of 6.83 dl / g was obtained. From this result, the ethylene polymer obtained in the above step (ii) has a density of 0.970 g / cm ³ and an intrinsic viscosity [η] of 1.38 dl / g (MFR;
6 g / 10 min), and the amount of polymerization was calculated to be 158 g. The results are shown in Table 1.

[0177]

Example 4 Production of Ethylene Polymer Composition (4) In step (i) of Example 3, a mixed gas of ethylene and 1-butene (1-butene content; 0.4
Polymerization was carried out for 0.2 hours (step (iii)), and in the step (ii), a mixed gas having a hydrogen content of 1.90 mol% was used as a mixed gas of ethylene and hydrogen. Polymerization was performed in the same manner as in Example 3 except that the polymerization was performed for 1.3 hours (step (iv)).

After the polymerization was completed, the polymer was filtered and then
Dry overnight at ° C. 250 g of ethylene polymer composition (4) was obtained. The obtained ethylene polymer composition (4) was melt-kneaded with a stabilizer in the same manner as in Example 3.

The density of the obtained ethylene polymer composition (4)
Degree is 0.962g / cm^ThreeAnd the MFR is 0.12g
/ 10 minutes (intrinsic viscosity [η]; 2.43 dl / g)
Was. In addition, as a result of performing only the above step (iii),
Density is 0.939g / cm^Three And the intrinsic viscosity [η] is
75 g of an ethylene-based polymer having a yield of 5.80 dl / g was obtained.
Was. This result indicates that the ethyl acetate obtained in step (iv) above
The ren-based polymer has a density of 0.972 g / cm^ThreeAnd
Intrinsic viscosity [η] is 1.00 dl / g (MFR; 50 g /
10 minutes), and the amount of polymerization was calculated to be 175 g.
Table 1 shows the results.

[0180]

Example 5 Production of Ethylene Polymer Composition (5) In Example 3, a prepolymerization catalyst (C) was used in place of the prepolymerization catalyst (B), and ethylene was used in step (i). , A mixed gas of ethylene and 1-butene (1-butene content; 0.476 mol%) was used for polymerization for 0.5 hour (step (v)), and ethylene and hydrogen were mixed in step (ii). Polymerization was performed in the same manner as in Example 3 except that a mixed gas having a hydrogen content of 1.0 mol% was used as the gas and the polymerization was performed for 1 hour (step (vi)).

After the polymerization was completed, the polymer was filtered and
Dry overnight at ° C. 150 g of ethylene polymer composition (5) was obtained. The obtained ethylene polymer composition (5) was melt-kneaded with a stabilizer in the same manner as in Example 3.

The ethylene polymer composition (5) obtained had a density of 0.957 g / cm ³ and an MFR of 0.038.
It was g / 10 minutes (intrinsic viscosity [η]; 2.63 dl / g).

As a result of performing only the step (v), 60 g of an ethylene polymer having a density of 0.938 g / cm ³ and an intrinsic viscosity [η] of 5.0 dl / g.
was gotten. From this result, the ethylene polymer obtained in the above step (vi) has a density of 0.960 g / cm ³ and an intrinsic viscosity [η] of 1.05 dl / g (MFR; 4).
It was calculated that the amount of polymerization was 90 g. The results are shown in Table 1.

[0184]

Example 6 Production of Ethylene Polymer Composition (6) In Example 3, the prepolymerization catalyst (B) was replaced with the prepolymerization catalyst (D), and the ethylene was replaced in step (i). , A mixed gas of ethylene and 1-butene (1-butene content; 0.313 mol%) was used for 0.5 hour polymerization (step (vii)), and ethylene and hydrogen were added in the step (ii). Polymerization was performed in the same manner as in Example 3 except that the mixed gas having a hydrogen content of 1.52 mol% was used as the mixed gas of 1) and the polymerization was performed for 1 hour (step (viii)).

After the polymerization was completed, the polymer was filtered and then
Dry overnight at ° C. 192 g of ethylene polymer composition (6) was obtained. The obtained ethylene polymer composition (6) was melt-kneaded with a stabilizer in the same manner as in Example 3.

The density of the obtained ethylene polymer composition (6)
Degree is 0.966g / cm^ThreeAnd the MFR is 0.044
g / 10 min (intrinsic viscosity [η]; 2.6 dl / g)
Was. In addition, as a result of performing only the above step (vii),
Density is 0.960 g / cm^Three And the intrinsic viscosity [η] is
77 g of ethylene-based polymer having 5.1 dl / g was obtained.
Was. Based on this result, the ethyl acetate obtained in the above step (viii)
The ren-based polymer has a density of 0.970 g / cm^ThreeAnd
Intrinsic viscosity [η] is 0.9 dl / g (MFR; 50g / 10
Min) and the amount of polymerization was calculated to be 115 g. Conclusion
The results are shown in Table 1.

[0187]

Comparative Example 1 Production of Ethylene Polymer Composition (7) In Example 1, 30 g of the ethylene polymer (5) was used in place of the ethylene polymer (1) to prepare the ethylene polymer (3). An ethylene polymer composition (7) was obtained in the same manner as in Example 1 except that 20 g of the ethylene polymer (6) was used instead.

The ethylene polymer composition (7) obtained had a density of 0.951 g / cm ³ and an MFR of 0.5 g / cm ^3.
It was 10 minutes. The results are shown in Table 1.

[0189]

[Table 1]

It can be seen that the ethylene polymer compositions obtained in Examples 1 to 6 are excellent in moldability, mechanical strength and rigidity, and ESCR.

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

Claims (5)

[Claims] 1. An (A) ethylene polymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-1) density (d _A ) is 0.96 to 0. .98 g / c
in the range of m ^3, 0.5 to the (A-2) the intrinsic viscosity [eta]
Ethylene polymer 20 to 9 in the range of 3.0 dl / g
0% by weight, (B) ethylene polymer or ethylene and 3 carbon atoms
A copolymer of 20 to 20 α-olefins (B-1)
The density (d _B ) is in the range of 0.91 to 0.965 g / cm ³ , and (B-2) the intrinsic viscosity [η] is 1.0 to 10 dl / g.
In the range of 80 to 10% by weight, wherein at least one of the (A) ethylene polymer and the (B) ethylene polymer is an ethylene-based polymer produced using a metallocene catalyst. a coalescing, (1) (a) the ratio of the density of the ethylene-based polymer (d _a) wherein (B) and the density of the ethylene-based polymer (d _B) (d _a /
d _B ) is larger than 1 and (2) the density is in the range of 0.940 to 0.970 g / cm ³ , and (3) the melt flow rate (MFR; 190 ° C., 2.16).
(measurement under kg load) is in the range of 0.005 to 20 g / 10 minutes, and (4) melt flow rate (MFR) and melt tension (MT) are log (MT) ≧ −0.4 log ( MFR) +0.7, and (5) an ethylene-based polymer composition characterized by having a diameter swell ratio of more than 1.35. 2. The ethylene-based polymer composition according to claim 1, wherein the ethylene-based polymer (A) and / or the ethylene-based polymer (B) is produced by using the following metallocene catalyst: [I] A transition metal compound represented by the following general formula (I): (Wherein, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, and R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; X ¹ and X ² may be the same or different from each other, and a part of a hydrogen atom may be bonded to a part of adjacent groups to form at least one ring together with the carbon atom to which those groups are bonded. Represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group; Hydrocarbon group, divalent silicon-containing group or 2
Shows a monovalent germanium containing group. ) [II] a compound capable of activating this transition metal compound [I], and (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst. 3. The ethylene-based polymer composition according to claim 1, wherein the ethylene-based polymer (A) and / or the ethylene-based polymer (B) is produced by using the following metallocene catalyst: [I] A transition metal compound represented by the following general formula (II) or a transition metal compound represented by the following general formula (III): (In the formula, M, X ¹ and X ² are the same as those in the general formula (I), and R ^{5 to} R ⁹ may be the same or different from each other, and at least two of them are methyl or ethyl. And the others are hydrogen atoms, and R ^{10 to} R ¹⁴ may be the same or different from each other, and at least 2
One or more is methyl or ethyl, and the others are hydrogen atoms. ) (In the formula, M, X ¹ and X ² are the same as those in the general formula (I), R ^{15 to} R ¹⁹ may be the same or different from each other, and four of them are methyl or ethyl. ,
And the others are hydrogen atoms, or 5 are methyl or ethyl, and R ²⁰ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ) [II] a compound capable of activating this transition metal compound [I], and (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst. 4. An ethylene polymer (A) or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-1) density (d _A ) is 0.96 to 0. .98 g / c
in the range of m ^3, 0.5 to the (A-2) the intrinsic viscosity [eta]
Ethylene polymer 20 to 9 in the range of 3.0 dl / g
0% by weight, (B) ethylene polymer or ethylene and 3 carbon atoms
A copolymer of 20 to 20 α-olefins (B-1)
The density (d _B ) is in the range of 0.91 to 0.965 g / cm ³ , and (B-2) the intrinsic viscosity [η] is 1.0 to 10 dl / g.
In the range of 80 to 10% by weight, wherein at least one of the (A) ethylene polymer and the (B) ethylene polymer is an ethylene-based polymer produced using a metallocene catalyst. a coalescing, (1) (a) the ratio of the density of the ethylene-based polymer (d _a) wherein (B) and the density of the ethylene-based polymer (d _B) (d _a /
d _B ) is larger than 1 and (2) the density is in the range of 0.940 to 0.970 g / cm ³ , and (3) the melt flow rate (MFR; 190 ° C., 2.16).
(measured under kg load) is in the range of 0.005 to 20 g / 10 minutes, and (4) melt flow rate (MFR) and melt tension (MT) are -0.4 log (MFR) + 0.7 ≥ log (MT) ≧ −0.4 log
(MFR) +0.1 is satisfied, and (5) diameter swell ratio exceeds 1.35, The ethylene polymer composition characterized by the above-mentioned. 5. The ethylene-based polymer composition according to claim 4, wherein the ethylene-based polymer (A) and / or the ethylene-based polymer (B) is produced by using the following metallocene catalyst: [I] a transition metal compound represented by the general formula (II) or a transition metal compound represented by the general formula (III), and [II] a compound capable of activating the transition metal compound [I]. And (II-1) organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.