JPH10195260A - Molded body made of polyethylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molded body made of a polyethylene. SOLUTION: This molded body made of a polyethylene is composed of an ethylene-based polymer composition which comprises (A) 20-90wt.% of an ethylene-based polymer having 0.95-0.98g/cm<3> density (dA) and 0.5-3.0dl/g intrinsic viscosity [η] and (B) 80-10wt.% of and an ethylene-based polymer having 0.91-0.965g/cm<3> density (dB) and 1.0-10dl/g intrinsic viscosity in which at least one of the components A and B is an ethylene-based polymer produced by using a metallocene catalyst. The composition has the ratio of DA and DB (DA/DB) of >1, 0.940-0.970g/cm<3> density, 0.005-20g/10 minutes MFR, in which MFR and melt tension(MT) satisfies the equation log(MT)>=-0.4 log(MFR)+0.7, and >1.35 diameter swell ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene molded article such as a hollow molded article, a pipe molded article, and an inflation film, and more particularly, to a molded article comprising a conventionally known ethylene polymer or an ethylene polymer composition. The present invention relates to a molded article made of polyethylene which is superior in mechanical strength and the like as compared with the above.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene homopolymer, ethylene
Polyethylene molded articles made of an ethylene-based polymer such as an α-olefin copolymer include small-sized containers such as cosmetic bottles, detergent bottles, kerosene cans, medium-sized containers such as industrial chemical cans,
It is widely used as hollow molded articles such as fuel tanks for automobiles and large containers such as drums, pipe molded articles such as sewer pipes, water pipes and gas pipes, and blown films used for shopping bags and the like in supermarkets.

[0003] Of these polyethylene molded articles, the hollow molded articles are blow molded by extruding a cylindrical molten resin (parison) from an annular die, then sandwiching the parison with a mold, and blowing and forming air. Manufactured. Generally, when a large container is blow-molded, the parison may hang down under its own weight (drawdown), or uneven thickness may occur during shaping, resulting in a poor shape of the molded body.
In order to reduce the drawdown, it is necessary to select an ethylene polymer having a large melt tension (melt tension). Further, in order to reduce the thickness deviation of the molded body or to improve the pinch-off shape of the molded body, it is necessary to select an ethylene polymer having a large swell ratio. Furthermore, the required properties of the hollow molded article include impact strength, E
SCR and the like have been mentioned, and recently, improvement in rigidity has been demanded for improving economy.

By the way, an ethylene polymer produced by a Ziegler-Natta type catalyst typified by a magnesium chloride-supported titanium catalyst has almost no long-chain branching and is excellent in rigidity and impact strength. Since the moldability is inferior to that of the ethylene-based polymer produced by the Cr-based Philips type catalyst, uneven thickness may occur during shaping. On the other hand, the ethylene copolymer produced by the high-pressure method and the ethylene copolymer produced by the Cr-based Phillips type catalyst have a lower melt tension and swell ratio than the ethylene copolymer produced by the Ziegler-Natta type catalyst. Since it is high, it has excellent moldability such as good pinch-off shape, but is inferior in rigidity and impact strength due to the presence of long chain branches.

[0005] Various methods have been proposed for improving the properties of such ethylene polymers. For example, JP-A-55-12735 describes 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 are described. 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.

For this reason, if a polyethylene hollow molded article having a better balance of mechanical strength and rigidity appears than a conventional hollow molded article made of an ethylene polymer, its industrial value will be extremely large.

[0007] Of the polyethylene molded articles, pipe molded articles are required to have pipe fatigue characteristics, mechanical strength, and the like. As a test of pipe fatigue characteristics, specifically, a hot internal pressure creep test, a notched tensile creep test, a notched tensile fatigue test, and the like are performed, and it is desirable that all of these have high performance. In recent years, improvement in rigidity has been demanded for economical improvement such as thinning of pipes, and formability has been demanded for reduction of power consumption.

By the way, polyethylene used for gas pipe applications at present has a medium density (density: 0.94).
0~0.945g / cm ³⁾ Many things, pipe fatigue properties, creep resistance moldability those somewhat superior, rigidity is not sufficient. Also, a method of improving creep resistance by cross-linking a pipe has been proposed, but the rigidity is not sufficient. Also, high-density polyethylene (density; around 0.950 g / cm ³ ) is being used for the purpose of improving rigidity, but sufficient pipe fatigue characteristics have not been obtained.

For this reason, if a polyethylene pipe molded article having a better balance of pipe fatigue characteristics, mechanical strength and rigidity than a conventional pipe molded article made of an ethylene polymer appears, its industrial value will be extremely large.

[0010] Of the polyethylene molded articles, blown films are required to have less uneven thickness and excellent mechanical strength. In order to prevent uneven thickness, it is necessary to improve the stability of the melt (bubble) of the tubular material extruded at the time of molding, and for this purpose, an ethylene polymer having a large melt tension (melt tension) is required. You need to choose.

By the way, ethylene polymers produced by a Ziegler-Natta type catalyst typified by a magnesium chloride-supported type titanium catalyst have almost no long-chain branching and excellent film impact strength. Used as a material for blown film,
Melt tension is low and moldability (bubble stability) is inferior to that of an ethylene polymer produced by an r-type Philips type catalyst. On the other hand, the ethylene polymer produced by the high-pressure method and the ethylene polymer produced by the Cr-Phillips type catalyst have higher melt tension and moldability than the ethylene polymer produced by the Ziegler-Natta type catalyst. But the impact strength is poor due to the presence of long chain branches.

A method for improving the properties of such an ethylene polymer is disclosed in Japanese Patent Application Laid-Open No. 55-12735,
It is described in JP-A-60-36546 and the like.
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.

For this reason, if a polyethylene blown film having a higher mechanical strength than a conventional blown film made of an ethylene polymer appears, its industrial value will be extremely large.

The inventors of the present invention have studied the ethylene polymer in view of such prior art, and found that a molded article made of an ethylene polymer produced using a specific metallocene catalyst has high moldability and mechanical properties. It was found to be excellent in strength and rigidity.

Further, as a result of further study, it has been found that a blend of a high-density ethylene polymer and a low-density ethylene polymer, wherein at least one of the ethylene polymers is produced using a metallocene catalyst. The molded article made of the ethylene polymer composition obtained was found to be excellent in mechanical strength, rigidity and the like, and completed the present invention.

[0016]

An object of the present invention is to provide a molded article made of polyethylene having excellent mechanical strength, such as a hollow molded article and a pipe molded article.
The purpose is to provide blown film and the like.

[0017]

The polyethylene molded article according to the present invention comprises: (A) an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-1) (A-2) an ethylene polymer 20 having a density (d _A ) in the range of 0.95 to 0.98 g / cm ³ and (A-2) an intrinsic viscosity [η] in the range of 0.5 to 3.0 dl / g and 90% by weight, the (B) a copolymer of ethylene homopolymer or ethylene and carbon atoms and 3 to 20 of the α- olefin, (B-1) density (d _B) 0.91 ~0.965g / cm ³
(B-2) 80 to 10% by weight of an ethylene polymer having an intrinsic viscosity [η] in the range of 1.0 to 10 dl / g, wherein the (A) ethylene polymer and ( B) At least one of the ethylene polymers is a polymer produced by using a metallocene catalyst, and (1) the density (d _A ) of the (A) ethylene polymer and the (B) ethylene polymer The ratio (d _A / d _B ) to the density (d _B ) of the coalescence is greater than 1; (2) the density is in the range of 0.940 to 0.970 g / cm ³ ;
(3) the melt flow rate (measured at 190 ° C. under a load of 2.16 kg) is in the range of 0.005 to 20 g / 10 minutes,
(4) Melt flow rate (MFR (g / 10 min)) and melt tension (MT (g)) are: log (MT) ≧ −0.4 log (MFR) +0.70 (5) The diameter swell ratio is It is characterized by comprising an ethylene-based polymer composition exceeding 1.35.

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 following general formula (i): [II] a compound capable of activating the transition metal compound [I], and (II-1) an organoaluminum compound; -
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]

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(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; 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. And a part of groups adjacent to each other may be bonded to form at least one ring together with the carbon atom to which those groups are bonded, and 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.) Further, the ethylene polymer as described above (A) and / or ethylene-based polymer (B) can also be prepared 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), and [II] a compound capable of activating the 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.

[0021]

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(Wherein, 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, and at least two or more thereof are methyl Or ethyl, the other being a hydrogen atom, and 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. )

[0023]

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(Wherein 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 Ethyl and the others are hydrogen atoms, or 5 are methyl or ethyl, and R ²⁰ and R ²¹ may be the same or different from each other, and have an alkyl group having 1 to 5 carbon atoms or In the present invention, examples of the molded article include a hollow molded article, a molded pipe, and an inflation film.

[0025]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polyethylene molded article according to the present invention will be specifically described. The polyethylene molded article according to the present invention is formed from an ethylene polymer composition (1) comprising the following ethylene polymer (A) and ethylene polymer (B).

The polyethylene molded article according to the present invention is formed from an ethylene polymer composition (1) comprising the following ethylene polymer (A) and ethylene polymer (B). , At least one of the ethylene-based polymer (A) and the ethylene-based polymer (B) is produced using a metallocene catalyst.

Ethylene Polymer (A) The ethylene polymer (A) is an ethylene homopolymer or a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

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

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

In the present invention, the composition of the ethylene polymer is ¹³
Determined by C-NMR spectrum. The ¹³ C-NMR spectrum of an ethylene polymer is usually determined by dissolving approximately 200 mg of a sample uniformly in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, and a pulse. It is measured under the conditions of a repetition time of 4.2 sec. And a pulse width of 6 μsec.

(A-1) Density of ethylene polymer (A) (d
_A ) is 0.95 to 0.98 g / cm ³ , preferably 0.96 to 0.98 g / cm ³ , more preferably 0.9 to 0.98 g / cm ³ .
It is in the range of 65 to 0.980 g / cm ³ .

In the present invention, the density of the ethylene polymer is
The strand obtained at the time of melt flow rate measurement described below is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured 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 1000 dl / g).
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 at 135 ° C. in decalin. 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 ethylene polymer (A) as described above is
It is preferably produced using a metallocene catalyst, and particularly preferably produced using a metallocene catalyst as described below.

Ethylene Polymer (B ) The ethylene polymer (B) is an ethylene homopolymer or a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Α- having 3 to 20 carbon atoms
Examples of the olefin include the same α-olefin as described above.

The ethylene polymer (B) contains units derived from ethylene in an amount of 60 to 100% by weight, preferably 80 to 100% by weight.
A unit derived from an α-olefin having 3 to 20 carbon atoms in a proportion of 0 to 40% by weight, preferably 2 to 20% by weight,
More preferably, the content is preferably 4 to 10% by weight.

(B-1) Density of ethylene polymer (B) (d
_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 dl / g (MFR; 35 to 0.
0003 g / 10 min), preferably 3.0 to 10 dl / g
It is.

The ethylene 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 Polymer At least one of the ethylene polymer (A) and the ethylene polymer (B) is produced using a metallocene catalyst. Both polymers (B) are preferably 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.

[0044]

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In the formula, M represents a transition metal atom belonging to 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.

R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other and represent a hydrogen atom, a halogen atom,
1-20 carbon atoms which may be substituted by halogen
A hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of adjacent groups is bonded to form a ring together with a carbon atom to which those groups are bonded. It may be formed. 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 silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylphenyl And 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. No.

Examples of the sulfur-containing group include a substituent in which the oxygen of the oxygen-containing compound has been replaced with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the nitrogen-containing group include an amino group, an amino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. And an arylamino group or an alkylarylamino group.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino. X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, an oxygen-containing group, a sulfur-containing group or It is 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 is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group. Specifically, as the divalent hydrocarbon group, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
Alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-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, Alkylsilylenes such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylenes, arylsilylene groups, and alkyldisilylenes such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene , An alkylaryldisilylene group, an aryldisilylene group, and the like.

Examples of the divalent germanium-containing group include compounds in which silicon of the above-mentioned divalent silicon-containing group is substituted 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, etc. No.

In the above examples, disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted. In addition, a transition metal compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten in the above zirconium compound can also be used.

Among the transition metal compounds represented by the general formula (i), a transition metal compound represented by the following general formula (ia) is preferable.

[0059]

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(Wherein M, R ¹ , R ³ , X ¹ , X ² and Y are the same as those in the formula (i), and R ^{22 to} R ²⁵ and R ⁴¹
To R ⁴⁴ may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group or an aryl group, the alkyl group or aryl group may be substituted by halogen or an organic silyl group. As the compound represented by the formula (ia), more specifically, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dibromide, dimethylsilylene-
Bis (indenyl) dimethylzirconium, 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.

Further, in the above-mentioned zirconium compounds, transition metal compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten can also be mentioned.

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

[0063]

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In the formula, M, X ¹ and X ² are the same as those 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, 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.

In addition, a transition metal compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten in the above zirconium compound can also be used.

[0067]

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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, and four of them are methyl or ethyl, and the other is a hydrogen atom, or five are methyl or ethyl.

R ²⁰ and R ²¹ may be the same or different and are 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 and (pentaethylcyclopentadienyl) (cyclopentadienyl). (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.

Further, in the above-mentioned zirconium compounds, transition metal compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten can also be mentioned.

Of these, those having a 5-substituted cyclopentadienyl ring and an unsubstituted cyclopentadienyl ring are particularly preferred. 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, for example, by the following general formula (iv). During ^{_{R a n AlX 3-n ...}} (iv) ( 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
3. ) In formula (iv), R ^a is the number of carbon atoms 1 to 1
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl And so on.

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.

As the organoaluminum compound (II-1), a compound represented by the following general formula (v) can also be used. ^{_{R a n AlY 3-n ...}} (v) ( wherein, R ^a is as defined above, Y is -OR ^b group, -
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
iR ^f ₃ or —N (R ^g ) AlR ^h ₂ ; n is 1 to 2; R ^b , R ^c , R ^d and R ^h are methyl,
Ethyl, isopropyl, isobutyl, cyclohexyl,
Phenyl and the like, ^Re is a hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl and the like, and ^Rf and ^Rg are methyl, ethyl 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 and 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 alone or in combination of two or more.
The aluminoxane (II-2) (hereinafter also referred to as “component (II-2)”) may be a conventionally known benzene-soluble aluminoxane, or a benzene as disclosed in JP-A-2-276807. It may be an insoluble organic aluminum oxy compound.

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 an 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 in producing the aluminoxane include the same compounds as those described above as the organoaluminum compound (II-1).

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Organoaluminum compounds can 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. Among these solvents, aromatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Insoluble or poorly soluble.

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

The aluminoxane (II-2) can be used alone or in combination of two or more. The compound (II-3) (hereinafter also referred to as “component (II-3)”) which forms an ion pair by reacting with the transition metal compound [I] includes:
JP-A-1-501950, JP-A-1-50203
No. 6, JP-A-3-179005, JP-A-3-179005
JP 179006, JP-A-3-207703,
JP-A-3-207704, USP-532110
The Lewis acids, ionic compounds and carborane compounds described in the specification of No. 6, etc. can be exemplified.

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 ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like.

These components (II-3) can be used alone or in combination of two or more. As the compound [II] capable of activating the transition metal compound [I], the components (II-1), (II-2) and (II-
Two or more compounds selected from 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 _Two, A
l_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, Ca
O, ZnO, BaO, ThO_TwoEtc or a mixture of these
Object, eg SiO_Two-MgO, SiO_Two-Al _TwoO_Three, Si
O_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three,
SiO_Two-TiO_Two-MgO or the like is used. Among these
Then, SiO_TwoAnd / or Al _TwoO_ThreeThe main component
Are preferred.

The above inorganic oxide contains a small amount of Na_TwoCO
_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoS
O_Four, Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg
(NO_Three) _Two, Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li
_TwoContains carbonate, sulfate, nitrate and oxide components such as O
It may be.

The carrier [III] has different properties depending on the type and the production method, but has a specific surface area of 50 to 1000 m.
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.

Such an inorganic carrier may be used, if necessary,
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 water adsorbed on the carrier (% by weight) 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 content (% by weight) = {(XY) / X} × 100 An organic compound can also be used as the carrier [III], for example, ethylene, propylene, 1-butene, 4-methyl Use of (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as -1-pentene or polymers or copolymers mainly composed of vinylcyclohexane and styrene Can be.

The catalyst preferably used for the production of the ethylene-based polymer (A) and the ethylene-based polymer (B) includes a carrier [III] as described above, which comprises a transition metal compound [I] and a component [II]. A supported metallocene catalyst (solid catalyst) supported.

[0097] The 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 brought into contact 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 the catalyst from these components, the transition metal compound [I] is used in an amount of usually 5 × 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 mol per 1 g of the carrier [III].
× 10 ^- used ⁴ molar quantities. In the component [II], the atomic ratio (Al or B / transition metal) of the transition metal compound [I] to aluminum or boron of the component [II] to the transition metal is usually 10 to 500, preferably 20 to 200. Used in quantity. When organoaluminum compound (II-1) and aluminoxane (II-2) are used as component [II], aluminum atom (Al-1) in component (II-1) and aluminum atom (Al-2) in component (II-2) Aluminum atom (Al-
It is desirable that the compound be used in such an amount that the atomic ratio (Al-1 / Al-2) of 2) becomes 0.02 to 3, more preferably 0.05 to 1.5.

These components are usually used at -50 to 150 ° C.
Preferably at a temperature of -20 to 120 ° C, usually for 1 minute to 50
The contact is carried out for a time, preferably 10 minutes to 25 hours. The solid catalyst prepared as described above has a transition metal compound [I] of 5 × 1 as a transition metal atom per 1 g of the support [III].
It is preferably carried in an amount of 0 ^{-6 to} 5 × 10 ^-4 gram atoms, and more preferably in an amount of 10 ^-5 to 2 × 10 ^-4 gram atoms. The component [I
I] is preferably carried in an amount of 10 ^{−3 to} 5 × 10 ⁻² gram atoms as aluminum or boron atoms per 1 g of the support [III], and more preferably 2 × 10 ⁻³ to 2 × 10 ^−2.
It is preferably carried in an amount of × 10 ^-2 gram atoms.

For the production of the ethylene-based polymer (A) and the ethylene-based polymer (B), the solid catalyst as described above can be used as it is, but the solid catalyst is prepolymerized with an olefin to prepare a prepolymerized catalyst. Can be used after forming.

The prepolymerized 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.

In 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 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 , in terms of transition metal per liter of polymerization volume.
It is desirable that the amount be from ² to ^10-2 mol, more preferably from 5 x ^10-5 to ^10-2 mol.

The prepolymerization is carried out at a temperature of usually -20 to 60 ° C, preferably 0 to 50 ° C, for 0.5 to 100 hours, preferably for about 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.

As the prepolymerization catalyst, an olefin may be introduced into a solid catalyst suspension prepared using an inert hydrocarbon solvent, or the solid catalyst formed in the inert hydrocarbon solvent may be converted from the suspension. After separation, the suspension may be suspended again in an inert hydrocarbon and the olefin may be introduced into the resulting suspension.

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

In the prepolymerized catalyst thus obtained, the transition metal compound [I] is about 5 × 10 ^{-6 to} 5 × 10 ^-4 gram atom, preferably 10 ^-5 gram atom as the transition metal per gram of the support [III]. In an amount of ~ 2 x 10 ^-4 gram atoms, 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.

The prepolymerization can be carried out either in a batch system or a continuous system, and can be carried out under reduced pressure, normal pressure or under 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 polymer (A) and the ethylene polymer (B), ethylene is homopolymerized in the presence of the solid catalyst or the prepolymerization catalyst as described above, or ethylene and another α- Copolymerize with olefin.

This (main) polymerization is carried out in suspension polymerization, slurry-like liquid phase or gas phase. In slurry polymerization,
The 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 slurry polymerization include the same as described above. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

The polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system.
In the (main) polymerization, the solid catalyst or the prepolymerized catalyst is usually a transition metal / liter (polymerization volume) of 10 ^-8 to 10 ^-3 gram atom / liter, and more preferably 10 ^-7 to 10 ^-4 gram atom / liter. It is desirable to use it in such an amount that

In the main polymerization carried out using a prepolymerization catalyst, component [II] not supported on a carrier may be added. Component [II] is based on the atomic ratio of aluminum or boron in component [II] to transition metal (Al or B /
Transition metal), 5 to 300, preferably 10 to 200,
More preferably, it can be used in an amount of 15 to 150.

The main polymerization can be carried out at a temperature of usually -50 to 200 ° C, preferably 0 to 100 ° C. In particular, when the ethylene polymer (A) is produced by a slurry polymerization method, it is usually 0 to 200 ° C, preferably 20 to 150 ° C.
It is desirable that the polymerization is carried out at a temperature of 50 ° C.
It is desirable to polymerize at a temperature of の 110 ° C.

When the ethylene-based polymer (B) is produced by a slurry polymerization method, it is desirable that the polymerization is usually carried out at a temperature of 0 to 200 ° C., preferably 20 to 150 ° C. It is desirable that the polymerization is carried out at a temperature of usually 50 to 120 ° C, preferably 60 to 110 ° C.

The polymerization pressure is usually from normal pressure to 100 kg / cm.
² , preferably under normal pressure to 50 kg / cm ² . The molecular weight of the resulting ethylene-based polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and polymerization pressure.

Composition The ethylene polymer composition (1) for forming the first polyethylene molded article according to the present invention comprises the ethylene polymer (A) and the ethylene polymer (B). 20 to 90% by weight, preferably 30 to 80% by weight, more preferably 40 to 75% by weight of the ethylene polymer (A), and 10 to 80% by weight of the ethylene polymer (B).
Preferably 20 to 70% by weight, more preferably 25 to 6% by weight.
It is contained in a proportion of 0% by weight.

The ethylene polymer composition (1)
Is, (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 greater than 1, preferably greater than 1 and 1.2
Hereinafter, it is more preferably formed from an ethylene-based polymer (A) and an ethylene-based polymer (B) in a range of from 1.005 to 1.08.

Such an ethylene polymer composition (1)
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 is 0.005 to
It is in the range of 20 g / 10 min, preferably 0.008 to 8 g / 10 min, more preferably 0.01 to 1.5 g / 10 min.
(3) The melt flow rate (MFR (g / 10 minutes)) value and the melt tension (MT (g)) value of the ethylene polymer composition (1) according to the present invention are represented by the following formula: log (MT) ≧ −0.4 log (MFR) +0.70.

The melt flow rate (MFR) value and the melt tension (MT) value of the ethylene polymer composition (1) satisfying the above relational expression are usually 1 to 100 g, preferably 2 to 50 g.

The melt tension (MT) is measured as a stress when a molten sample is stretched at a constant speed. 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-based polymer composition (1) having such a diameter swell ratio is excellent in moldability. For example, when the ethylene-based polymer composition (1) is blow-molded, a hollow molded body having excellent strength can be obtained because of its good pinch-off shape. Furthermore, since the thickness distribution of the hollow molded body can be narrowed, the weight per unit area can be reduced, and a hollow molded body with excellent buckling strength can be obtained with the same basis weight.

The swell ratio can be measured as follows. A tubular nozzle (inner diameter (D ₀ ) 3 mm, outer diameter 4 mm, length 10 mm) was attached to Capillograph-1B (manufactured by Toyo Seiki Seisakusho, barrel diameter 10 mm), and the barrel (the part where the sample was placed) was heated to 200 ° C. Warm,
Hold. Approximately 10 g of a sample is put in a barrel, a piston is attached, air bubbles are removed, and then preheating is performed for 6 minutes. After preheating, the sample was extruded at each piston speed of 10, 20, 30, 50, 75 (mm / min) and 15 m from the nozzle outlet
The strand diameter (D _i ) below m is measured with a laser beam.

The ratio (SR _i = D _i / D ₀ ) between the strand diameter (D _i ) and the tube nozzle diameter (D ₀ ) at each piston speed measured in this way is calculated on a semi-logarithmic graph paper. From the curve obtained by plotting for each piston speed, the SR value at a piston speed of 50 (mm / min) is read, and this SR value is defined as the diameter swell ratio. It should be noted that the shear speed can also be obtained according to the piston speed.

The ethylene-based polymer composition (1) contains a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fogging agent as long as the object of the present invention is not impaired. Additives such as a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antioxidant, a hydrochloric acid absorbent, and an antioxidant may be added as necessary.

In the ethylene polymer composition (1), the ethylene polymer (A) and the ethylene polymer (B) are selected so as to satisfy the above-mentioned properties, and are blended by a known method. Alternatively, it can be directly produced by polymerization.

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

As a method for directly producing an ethylene polymer composition comprising the ethylene polymer (A) and the ethylene polymer (B) by polymerization, for example, a two-stage polymerization process is used. (A) is polymerized,
It can be produced by polymerizing the ethylene polymer (B) in the subsequent stage, or polymerizing the ethylene polymer (B) in the previous stage and polymerizing the ethylene polymer (A) in the subsequent stage.

Further, using a plurality of polymerization reactors, one of the polymerization reactors is used to polymerize the ethylene polymer (A), and then the other is used in the presence of the ethylene polymer (A). The polymer (B) is polymerized, or the ethylene polymer (B) is polymerized in one polymerization vessel, and then the ethylene polymer (B) is polymerized in the other polymerization vessel in the presence of the ethylene polymer (B). It can also be produced by polymerizing A).

Molded article The first polyethylene molded article according to the present invention can be obtained by subjecting the ethylene polymer composition (1) obtained as described above to various molding methods such as blow (injection), injection blow, and extrusion. It is obtained by molding using

The polyethylene hollow molded body can be manufactured by a conventionally known blow molding apparatus. As the molding conditions, conventionally known conditions can be adopted. For example, in the case of extrusion blow molding, a resin temperature of 100 ° C. to 3 ° C.
The ethylene-based polymer composition (1) is extruded from a die at 00 ° C. in a molten state, and then the parison is extruded. The parison is held in a mold having a shape to be applied. Attach to a mold at ℃ to obtain a hollow molded product. The stretching ratio is desirably 1.5 to 5 times in the transverse direction.

In the case of injection blow molding, a resin temperature of 10
The ethylene-based polymer composition (1) is injected into a mold at 0 ° C. to 300 ° C. to form a parison. Then, the parison is held in a mold having a shape to be applied, and air is blown into the parison. It is mounted on a mold at a temperature of from 300C to 300C to obtain a hollow molded body. The stretching ratio is desirably 1.1 to 1.8 times in the longitudinal direction and desirably 1.3 to 2.5 times in the lateral direction.

The polyethylene hollow molded article according to the present invention has less uneven thickness and is excellent in mechanical strength, rigidity and the like. Examples of the hollow molded body include small containers such as cosmetic bottles and detergent bottles, medium containers such as kerosene cans and industrial chemical cans, and large containers such as fuel tanks for automobiles and drums.

[0135] A polyethylene pipe molded product can be obtained by processing by a usual extrusion molding method. The polyethylene pipe molded article according to the present invention is excellent in pipe fatigue properties, mechanical strength, and the like.

The blown film made of polyethylene can be produced by a usual inflation molding method. The polyethylene blown film according to the present invention has less uneven thickness and is excellent in mechanical strength and the like.

[0137]

The polyethylene molded article of the present invention is formed from an ethylene polymer composition obtained by blending an ethylene polymer (A) and an ethylene polymer (B) having different densities. And has excellent mechanical strength and rigidity.

[0138]

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 are evaluated as follows. [Blow Molding Test] Using a blow molding machine, blow molding was performed at a molding temperature of 210 ° C. to form a blow bottle having a basis weight of 1.3 kg, and its moldability (drawdown and pinch-off shape) was examined. The number of times the bottle was broken by repeatedly dropping from a height of 6 m under the conditions was tested.

[Pipe Forming Test] The ethylene copolymer composition was processed at a processing temperature of 200 ° C. and a nominal diameter of 50 by a single screw extruder (manufactured by Ikegai Co., Ltd.) having a diameter of 65 mm · L / D = 25.
mm and a wall thickness of 5 mm.

[Hot internal pressure creep test] JIS K67
74 polyethylene tube for gas (nominal diameter 50mm, 1
The test was conducted according to the same standard using a pipe conforming to the above-mentioned standard. However, the hoop stress was performed at 59 kg / cm ² .

[Circumference notch tensile creep test] JIS
The test was performed according to Appendix K6774. However,
The applied stress was 80 kg / cm ² .

[Izod Impact Test (IZ)] JIS
The test was performed according to K7110. Test temperature is -30
C. was performed. [Inflation film molding test] Using a 20 mm small extruder, molding temperature 220 ° C, frost line height 30m
An inflation film having a m of 2 and a swelling ratio of 2 and a thickness of about 30 μm was formed, and the bubble stability was examined and the film impact strength was examined.

[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 reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 ml of toluene.
86 ml of a toluene solution of dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride (Zr; 0.00223 mmol / ml) was added to the 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. 9.5 ml of a triisobutylaluminum decane solution (1 mmol / ml) was added to the system, and prepolymerization of ethylene was carried out at 35 ° C. for 1.5 hours to contain 2.0 mg of zirconium per 1 g of the solid catalyst. Prepolymerized catalyst (A) in which 3 g of an ethylene polymer has been prepolymerized
I got

[0147]

[Synthesis Example 2] [Preparation of solid catalyst (b)] In Synthesis Example 1, bis (1,2) was used instead of the toluene solution of dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride.
3-dimethylcyclopentadienyl) zirconium dichloride in toluene solution (Zr; 0.00778 mmol /
solid catalyst (b) was obtained in the same manner as in Synthesis Example 1 except that 24 ml of the same was used.

[Preparation of Preliminary Polymerization Catalyst (B)] Except that solid catalyst (b) was used instead of solid catalyst (a), the same procedure as in the preparation of prepolymerization catalyst (A) was carried out, and per 1 g of solid catalyst was used. A prepolymerized catalyst (B) containing 2.3 mg of zirconium and prepolymerized with 3 g of an ethylene polymer was obtained.

[0149]

Example 1 Production of Ethylene-Based Polymer Composition (a) One liter of hexane was charged into a 2-liter stainless steel autoclave 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 of the prepolymerized catalyst (A) and 0.005 mmol in terms of zirconium atoms 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 instead, a mixed gas of ethylene and hydrogen (hydrogen content: 0.7 mol%) was introduced, and the polymerization was further performed at 80 ° C. for 1 hour (step (ii)). )).

After completion of the polymerization, the polymer was filtered,
Dried at C overnight. 264 g of an ethylene-based polymer composition (a) was obtained. Next, 50 g of the ethylene polymer composition (a) and a phenolic heat stabilizer (Irganox)
1076, 0.05 g from Ciba-Geigy Co., Ltd., 0.02 phosphorus heat-resistant stabilizer (Irgafos168, Ciba-Geigy Co., Ltd.) 0.02
After dry-blending 5 g, the mixture was melt-kneaded at 200 ° C. using a batch type kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.). Ethylene polymer composition (a) obtained
Has a density of 0.958 g / cm ³ and an MFR of 0.0
It was 2 g / 10 min (intrinsic viscosity [η]; 3.57 dl / g).

As a result of performing only the operation of the above step (i), the ethylene polymer 10 having a density of 0.941 g / cm ³ and an intrinsic viscosity [η] of 6.83 dl / g was obtained.
6 g were obtained. From this result, the ethylene polymer obtained in the above step (ii) has a density of 0.970 g / cm.
³ , and the intrinsic viscosity [η] is 1.38 dl / g (MF
R; 5.6 g / 10 min), and the polymerization amount was calculated to be 158 g. Table 1 shows the results.

A blow molding test was performed using this ethylene polymer composition (a). Both the drawdown resistance and the pinch-off shape were good, and a blow bottle with less uneven thickness was obtained. Further, physical properties of the obtained blow bottle were tested.

[0154]

Example 2 Preparation of Ethylene Polymer Composition (b) In Example 1, a prepolymerized catalyst (B) was used in place of the prepolymerized catalyst (A), and in step (i), ethylene was used instead of ethylene. The polymerization was carried out for 0.5 hours using a mixed gas of ethylene and 1-butene (1-butene content: 0.476 mol%) (step (iii)), and mixing of ethylene and hydrogen in step (ii) Polymerization was carried out in the same manner as in Example 1 except that polymerization was carried out for 1 hour using a mixed gas having a hydrogen content of 0.20 mol% as a gas (step (iv)).

After completion of the polymerization, the polymer was filtered,
Dried at C overnight. 150 g of the ethylene polymer composition (b) was obtained. Next, the mixture was melt-kneaded with the stabilizer in the same manner as in Example 1 using the ethylene polymer composition (b). The density of the obtained ethylene polymer composition (b) was 0.957 g / cm ³ , and the MFR was 0.038 g / cm ^3.
It was 10 minutes (intrinsic viscosity [η]; 2.63 dl / g).

The operation of only the above step (iii) was performed.
As a result, the density was 0.938 g / cm^Three Is the intrinsic viscosity
60 g of an ethylene polymer having [η] of 5.0 dl / g
was gotten. According to this result, the result obtained in the above step (iv) is obtained.
Ethylene polymer has a density of 0.960 g / cm^Threeso
And an intrinsic viscosity [η] of 1.05 dl / g (MFR; 4
0 g / 10 min), and the polymerization amount was calculated to be 90 g.
Was. Table 1 shows the results.

Using this ethylene polymer composition (b), an inflation film molding test was performed. Bubble stability during inflation molding was good, and an inflation film with less uneven thickness was obtained. In addition, physical properties of the obtained blown film were tested.

Using the ethylene polymer composition (b),
Pipe molding test A molding test was performed. The formability of the pipe was good. Further, physical properties of the obtained pipe were tested.

[0159]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 23:00 B29L 7:00 22:00 23:00

Claims (6)

[Claims] (A) An ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A-1) the density (d _A ) is 0.95 to in the range of 0.98 g / cm ^3, ethylene polymer and 20 to 90% by weight in the range of (a-2) the intrinsic viscosity [eta] is 0.5~3.0dl / g, (B) ethylene a copolymer of homopolymer or ethylene and carbon atoms 3 to 20 α- olefin, (B-1) density (d _B) is 0.91~0.965g / cm ³
(B-2) an ethylene polymer having an intrinsic viscosity [η] of 1.0 to 10 dl / g in an amount of 80 to 10% by weight, wherein (A) the ethylene polymer and ( B) At least one of the ethylene polymers is a polymer produced by using a metallocene catalyst, and (1) the density (d _A ) of the (A) ethylene polymer and the (B) ethylene polymer The ratio (d _A / d _B ) to the density (d _B ) of the union is larger than 1 (2)
Density is in the range of 0.940~0.970g / cm ^{3, (3)} a melt flow rate (190 ° C., 2.16 kg
(4) Melt flow rate (MFR (g / 10 minutes)) and melt tension (MT (g)) are log (MT) ≧ − 0.4 log (MFR) +0.7 is satisfied, and (5) the diameter swell ratio is 1.35.
A molded article made of polyethylene, comprising an ethylene-based polymer composition having a content of more than 1%. 2. The polyethylene molded article according to claim 1, wherein the ethylene-based polymer (A) and / or the ethylene-based polymer (B) is produced using the following metallocene catalyst; I] a transition metal compound represented by the following general formula (i): [II] a compound capable of activating the transition metal compound [I], and (II-1) an organoaluminum compound;
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; (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. ) 3. The polyethylene molded article according to claim 1, wherein the ethylene polymer (A) and / or the ethylene polymer (B) is produced 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): [II] a compound capable of activating the 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; (Wherein, 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 or more thereof are methyl or ethyl. And other are hydrogen atoms, and R ^{10 to} R ¹⁴ may be the same or different from each other, and at least two or more of them are methyl or ethyl and the others are hydrogen atoms. (Wherein, 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 ethyl. And the others are hydrogen atoms, or 5 are methyl or ethyl, and R ²⁰ and R ²¹ may be the same or different from each other, and may be an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. is there.) 4. The polyethylene molded article according to claim 1, wherein said molded article is a hollow molded article. 5. The polyethylene molded article according to claim 1, wherein the molded article is a pipe molded article. 6. The polyethylene molded article according to claim 1, wherein said molded article is an inflation film.