JPH0995571A - Modifier for high-density polyethylene and resin composition for blow molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modifier for a high-density polyethylene resin excellent in moldability, mechanical strengths, and stiffness by polymerizing ethylene using a catalyst contg. a metallocene compd. and to obtain a resin compsn. for blow molding contg. the modifier. SOLUTION: This modifier, comprising an ethylene polymer which may contain less than 10mol% 3-6C α-olefin units and has a density of 0.92-0.98g/cm<3> and an intrinsic viscosity [η] of 0.4-10dl/g, is obtd. by polymerizing ethylene in the presence of a catalyst contg. a metallocene compd. represented by the formula (wherein M is a transition metal atom of the groups IV-VIB; R<1> to R<4> are each H, a halogen, a 1-20C hydrocarbon group, or a silicon-, oxygen-, sulfur-, or phosphorus-contg, group; X<1> and X<2> are each H, a halogen, a 1-20C hydrocarbon or halohydrocarbon group, or an oxygen-or sulfur-contg. group; and Y is a divalent silicon-or germanium-contg. group or an alkylene).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modifier for high density polyethylene which has a high melt tension and a large diameter swell ratio and is excellent in mechanical strength and rigidity.

[0002]

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

Such an ethylene polymer is required to have various characteristics depending on the use or the molding method. Especially when producing industrial cans, drums, bottles, etc. by blow molding, the swell ratio (diameter swell ratio) is used. It is necessary to improve the pinch-off shape by using an ethylene polymer having a large). If an ethylene polymer having a large diameter swell ratio) is used, a blow molded product having a narrow wall thickness distribution can be obtained. 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.

Further, a modified product of an ethylene-based polymer produced by a Ziegler-Natta type catalyst has also been proposed. For example, a modified product of polyethylene using a radical generator (Japanese Patent Laid-Open No. 59-89341) and polyethylene. A maleic acid-modified product (JP-A-59-164347) and the like have been proposed.

However, such a modified ethylene-based polymer has improved moldability as compared with the unmodified ethylene-based polymer, but has reduced rigidity and impact strength. Therefore, it is desired to develop a modifier for high-density polyethylene, which has a high melt tension and swell ratio, is excellent in moldability, and is also excellent in mechanical strength and rigidity.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and includes a modifier for high density polyethylene which is excellent in moldability, mechanical strength and rigidity, and the modifier. It is intended to provide a resin composition for blow molding.

[0009]

SUMMARY OF THE INVENTION The modifier for high density polyethylene according to the present invention contains [A] (1) a unit derived from an α-olefin having 3 to 6 carbon atoms in an amount of less than 10 mol%. Often,
(2) The density is 0.92 to 0.98 g / cm ³ , and (3)
The intrinsic viscosity [η] is 0.4 to 10 dl / g, and (4)
It is characterized by being composed of an ethylene polymer produced by using a catalyst containing a metallocene compound represented by the following general formula.

[0010]

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(In the formula, M is a transition metal atom of Groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, halogen atoms, and C 1-20 carbon atoms. Hydrocarbon radical,
It is 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 some of the groups adjacent to each other are bonded to each other to form these groups. At least one ring may be formed with a carbon atom to be bonded, X ¹ and X ² may be the same or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, It is a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a divalent silicon-containing group, a divalent germanium-containing group, or an alkylene group. ).

The blow molding resin composition according to the present invention comprises:
It is composed of the above-mentioned [A] ethylene-based polymer and [B] high-density polyethylene for blow molding other than the above [A]. The above high-density polyethylene [B] has (1) 1 unit derived from an α-olefin having 3 to 6 carbon atoms.
(2) having a density of 0.94 to 0.98 g / cm ³ , (3) having an intrinsic viscosity [η] of 0.4 to 10 dl / g, and (4) It is preferably produced using a titanium-based Ziegler catalyst. In the blow molding resin composition, the amount ratio of the [A] ethylene polymer to the [B] high density polyethylene is [A]:
[B] = 5 to 50% by weight: 95 to 50% by weight is desirable. In a blow molding resin composition, its melt flow rate (MFR) value and melt tension (MFR)
T) value means the expression log [MT] ≧ −0.4log [M
FR] +0.70 and the radial swell (SR) ratio is preferably 1.35 or more. The blow-molded article according to the present invention is obtained by blow-molding the above-described blow-molding resin composition.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The modifier for high-density polyethylene and the resin composition for blow molding according to the present invention will be specifically described below. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. Sometimes used in a meaning.

[0014] High density polyethylene reforming material according to high-density polyethylene for modifier present invention is characterized in that it consists as follows [A] ethylene-based polymer. (1) The ethylene-based polymer [A] is an α-carbon compound having 3 to 6 carbon atoms.
-A unit derived from an olefin may be contained in an amount of less than 10 mol%, and specifically it is an ethylene homopolymer or a random copolymer of ethylene and an α-olefin. Α-C3 to C6 copolymerized with ethylene
Examples of the olefin include propylene, 1-butene,
Examples include 1-pentene, 1-hexene, 4-methyl-1-pentene and combinations thereof.

The ethylene polymer [A] has such an α
-Units derived from olefins may be contained in an amount of less than 10 mol%, preferably 0-5 mol%, more preferably 0-3 mol%.

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 1500
It is measured under the conditions of Hz, pulse repetition time of 4.2 sec. And pulse width of 6 μsec.

(2) The density of the ethylene polymer [A] is
0.92 to 0.98 g / cm ³ , preferably 0.9
³ to 0.975 g / cm ^3, more preferably 0.94 to 0.9.
It is 7 g / cm ³ . The density of the ethylene-based polymer may be measured by a density gradient tube after heat-treating the strand obtained at the time of measuring the melt flow rate described below for 1 hour at 120 ° C. and gradually cooling to room temperature over 1 hour. it can.

(3) The intrinsic viscosity [η] of the ethylene polymer [A] (measured in decahydronaphthalene at 135 ° C.) is 0.4 to 10 dl / g, preferably 1.
It is 0 to 8 dl / g.

The melt flow rate (MFR) of the above ethylene polymer [A] is 0.001 to 100 g / 10.
Minutes, preferably 0.005 to 50 g / 10 minutes. Melt flow rate (MFR) is ASTM
It is measured according to D1238-65T (190 ° C, under 2.16 kg load).

(4) The ethylene polymer [A] is produced using a catalyst containing the metallocene compound [I] represented by the following general formula (I). FIG. 1 shows a process for producing an ethylene polymer [A] using a metallocene catalyst.

[0021]

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In the formula, M is a transition metal of Groups IV to VIB of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, preferably titanium. , Zirconium and hafnium, particularly preferably zirconium.

Substituents R ^{1 to} R ⁴ R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other, and are each a hydrogen atom, a halogen atom, or a carbon number 1 to which a halogen may be substituted. 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, and a ring together with carbon atoms to which some of the groups adjacent to each other are bonded to each other. May be formed. It should be noted that each two R ¹ displayed
To R ⁴ indicate that when they are bonded to each other to form a ring, they are preferably bonded by a combination of the same symbols, for example, R ¹ and R ¹ are bonded to each other to form a ring. Indicates that is preferable.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine. 1-20 carbon atoms
The hydrocarbon group of, for example, 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 and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and propylphenyl, Biphenyl, α- or β
-Aryl groups such as naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Fused rings such as indene rings, benzene rings, naphthalene rings,
Examples include a group in which a hydrogen atom on a condensed ring group such as an acenaphthene ring or an indene ring is substituted with an alkyl group such as methyl, ethyl, propyl, or butyl.

Further, these hydrocarbon groups may be substituted with halogen. As the silicon-containing group, a monohydrocarbon-substituted silyl group such as methylsilyl or phenylsilyl,
Dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbons Examples thereof include silyl ethers of hydrocarbon-substituted silyl such as substituted silyl and trimethylsilyl ether, silicon-substituted alkyl groups such as trimethylsilylmethyl, and silicon-substituted aryl groups such as trimethylphenyl.

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.

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

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.

[0030]X ¹ and X ²  X¹And X²May be the same or different from each other
Substituted with hydrogen atom, halogen atom, halogen
A hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, or
Is a sulfur-containing group. As these atoms or groups
Is, specifically, R ¹~ R^FourOr an atom like
The same as the group can be mentioned.

Y Y is a divalent silicon-containing group, a divalent germanium-containing group, or an alkylene group. Specific examples of the divalent silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenyl. Alkylsilylene such as silylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, etc. Examples thereof include disilyl, alkylaryldisilyl and aryldisilyl groups. Examples of the divalent germanium-containing group include compounds in which silicon in the divalent silicon-containing group is replaced with germanium. As the alkylene group, for example, methylene, ethylene, propylene, butylene and the like having 1 carbon atom.
To 20 alkylene groups.

Examples of such metallocene compound [I] include dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl). Zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis ( Indenyl) zirconium dibromide, dimethylsilylene bis (indenyl) dimethyl zirconium, dimethyl Rylene bis (indenyl) diphenyl zirconium, dimethyl silylene bis (indenyl) methyl zirconium monochloride, dimethyl silylene bis (indenyl) zirconium bis (methane sulfonate), dimethyl silylene bis (indenyl) zirconium bis (p-toluene sulfonate), dimethyl silylene Bis (indenyl) zirconium bis (p-toluenesulfonato), dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (indenyl) zirconium trifluoromethanesulfonato, dimethylsilylenebis (4,5,6) , 7-
Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis ( Indenyl)
Examples include zirconium dichloride.

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 metallocene compound in which zirconium metal is replaced with titanium metal or hafnium metal can be given. Among these, the metallocene compound represented by the following formula (Ia) is preferably used.

[0034]

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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 are 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 ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, and dimethylsilylenebis (2-methylindenyl) zirconium dichloride. , Dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride and the like.

In the present invention, the ethylene polymer [A]
The catalyst used in the production of [I] is as described above.
The catalyst comprises a metallocene compound, and the catalyst is [II] a metallocene compound, [II] a compound capable of activating the metallocene compound [I], and (II-1) an organoaluminum compound, (I
I-2) an organoaluminum oxy compound, and (II-3) at least one compound selected from compounds that react with the metallocene compound [I] to form an ion pair, and [III] a fine particle carrier It is preferable to use a carrier-supported metallocene catalyst.

The cocatalyst components are shown below. The organoaluminum compound (II-1) used in the present invention is represented by, for example, the following general formula (i). R ¹ _n AlX _3-n (i) (in the formula (i), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
It is 3. In the above general formula (i), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-
Propyl, isopropyl, isobutyl, pentyl, hexyl, 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.

As the organoaluminum compound (II-1), a compound represented by the following general formula (ii) can also be used. R ¹ _n AlY _3-n (ii) (In the formula (ii), R ¹ is the same as above, and Y is -OR.
² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. Specific examples include the following compounds. (1) compounds represented by R ¹ _n Al (OR ² ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al
(OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc.
(3) A compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso
-Bu) _{2 and the} like, (4) compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe,
Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂
(5) R ¹ _n Al (SiR ⁶ ₃ ) _3-n such as AlN (SiMe ₃ ) ₂
A compound represented by, for example, (iso-Bu) ₂ AlSi Me ₃
Such as (6) a compound represented by R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-
Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among these, the general formulas R ¹ ₃ Al, R ¹ _n
Compounds represented by Al (OR ² ) _3-n and R ¹ _n Al (OAlR ⁴ ₂ ) _3-n are preferable, and R is an isoalkyl group, and n is particularly preferable.
Compounds with = 2 are preferred.

It is also possible to use these in combination.
The (II-2) organoaluminum oxy compound used in the present invention may be a conventionally known benzene-soluble aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807. It may be a 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, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (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 in the production of the aluminoxane include the same ones as shown above as the organoaluminum compound (II-1).

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable. The organoaluminum compound (II-2) 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.

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

The solubility of such an organoaluminum oxy compound in benzene is 10 times that of the organoaluminum oxy compound corresponding to 100 mg of Al.
After suspending in 0 ml of benzene and mixing under stirring at 60 ° C for 6 hours, the solid portion separated on the filter was subjected to filtration at 60 ° C using a jacketed G-5 glass filter while hot. Amount of Al atoms present in all the filtrates after washing 4 times with 50 ml of benzene at ℃ (x
It is determined by measuring (mmol) (x%).
The compound (II-3) which reacts with the metallocene compound [I] used in the present invention to form an ion pair (hereinafter referred to as component (II
-3)), JP-A-1-501950, JP-A-1-502036, and JP-A-3-179.
Examples of Lewis acids, ionic compounds and carborane compounds described in JP-A No. 005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-547718 and the like. You can

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 -Al 2
O _{3 and the} like can be mentioned.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 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, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be mentioned.

These may be used in combination of two or more kinds. In the present invention, as the compound [II] capable of activating the metallocene compound [I], the above-mentioned component (II
-1), (II-2) or (II-3) can also be used in combination.

In the present invention, the [III] carrier has a particle size of 1
0 to 300 μm, preferably 20 to 200 μm granular
A fine particle solid is used. As this carrier,
A porous inorganic oxide is preferably used, specifically, Si
O₂, Al₂O_Three, MgO, ZrO₂, TiO₂, B₂O_Three, Ca
O, ZnO, BaO, ThO₂Or a mixture of these,
For example, SiO₂-MgO, SiO₂-Al₂O_Three, SiO₂-Ti
O ₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-
MgO or the like is used. Among them, SiO₂And
And / or Al₂O_ThreeThe main component is preferably.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂
(SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO
₃ ) ₃ , carbonates such as Na ₂ O, K ₂ O and Li ₂ O, sulfates, nitrates and oxides may be contained.

In the present invention, the properties vary depending on the type and production method, but the specific surface area is 50 to 1000 m ² / g, further 100 to 700 m ² / g, and the pore volume is 0.3.
A carrier of ˜2.5 cm ³ / g is 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 carrier used in the present invention [II
The amount of adsorbed water of [I] is preferably less than 1.0% by weight, and more preferably less than 0.5% by weight. The surface hydroxyl group content is preferably 1.0% by weight or more, more preferably 1.5 to 4.0% by weight, and particularly 2.0 to 3.0.
Preferably it is 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 amount (% by weight) = {(X−Y) / X} × 100

In the present invention, an organic compound may be used as the carrier [III], for example, an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. A (co) polymer produced as a main component or a polymer or copolymer produced as vinylcyclohexane or styrene as a main component can be used.

The catalyst used in the present invention comprises a metallocene compound [I] and a component [II] on a carrier [III] as described above.
A carrier-supported metallocene catalyst (solid catalyst) in which and are supported is desirable.

This solid catalyst can be prepared by contacting the components [I], [II] and [III] in any order, but preferably the component [II] and the carrier [III] are mixed and contacted. It is preferable that the metallocene compound [I] is mixed and brought into contact with the metallocene 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 metallocene compound [I] is usually used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, and preferably 10 ⁻⁵ to ⁵ mol, per 1 g of the carrier [III].
Used in an amount of 2 × 10 ⁻⁴ mol. 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 metallocene compound [I], and is usually 10 to 500, preferably 20 to 200.
Used in amounts. As the component [II], an organoaluminum compound (II-1) and an organoaluminum oxy compound (II
-2) is used, the aluminum atom (Al-1) in (II-1) and the aluminum atom (Al-2 in (II-2) (Al
-2) is preferably used in an amount such that the atomic ratio (Al-1 / Al-2) is 0.02 to 3, more preferably 0.05 to 1.5.
Each of these components is usually -50 to 150 ° C, preferably-
1 minute to 50 hours at a temperature of 20 to 120 ° C., preferably 1
Contact for 0 minutes to 25 hours.

The solid catalyst prepared as described above is
The metallocene compound [I] is preferably carried in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom as a transition metal atom, and more preferably 10 ⁻⁵ to 2 ×, per 1 g of the carrier (c).
More preferably, it is supported in an amount of 10 ⁻⁴ gram atom. The component [II] is 10 ^{-3 to} 5 × 10 ^-2 as aluminum atom or boron atom per 1 g of the carrier [III].
It is desirable to be supported in the amount of gram atom, and more preferable to be supported in the amount of 2 × 10 ⁻³ to 2 × 10 ⁻² gram atom.

In the present invention, the solid catalyst as described above can be used as it is for the (main) polymerization of ethylene. However, it is also possible to preliminarily polymerize an olefin on this solid catalyst to form a prepolymerized catalyst before use. it can.

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.

In the prepolymerization, the metallocene compound [I] is usually used in an amount of 5 × 10 ^{−6 to} 5 per 1 g of the carrier [III].
It is used in an amount of x10 ^-4 mol, preferably 10 ^-5 to 2 x 10 ^-4 mol. The component [II] is the atomic ratio of aluminum or boron in the component [II] to the transition metal in the metallocene compound [I] (Al or B / transition metal), and is usually 1
It is used in an amount of 0 to 500, preferably 20 to 200.
When the organoaluminum compound (II-1) and the organoaluminum oxy compound (II-2) are used as the component [II], the aluminum atom (Al-1) and (I
I-2) atomic ratio of aluminum atoms (Al-2) in (Al-1
/ Al-2) is preferably 0.02 to 3, more preferably 0.05 to 1.5.

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

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. Examples of the prepolymerized olefin include ethylene and the above-mentioned carbon atoms having 3 to 6 carbon atoms.
.Alpha.-olefin can be used, and these may be copolymerized.

The prepolymerization catalyst may be prepared by introducing an olefin into a solid catalyst suspension prepared by using an inert hydrocarbon solvent, or by preparing a solid catalyst produced in an inert hydrocarbon solvent from 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 metallocene 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, the 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.

In the present invention, the carrier [II
I] 0.1 to 500 g per 1 g, preferably 0.2 to 30
It is desirable that an olefin polymer (prepolymer) is produced in an amount of 0 g, more preferably 0.5 to 200 g.

In the prepolymerized catalyst thus obtained, the metallocene compound [I] is present as a transition metal in an amount of about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 1 g of the carrier [III]. In an amount of 2 × 10 ⁻⁴ gram atom, component [II] is the molar ratio of aluminum or boron in component [II] to the transition metal (Al or B / transition metal),
It is desirable that the carrier is supported in an amount of 5 to 200, further 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, hydrogen is allowed to coexist and the intrinsic viscosity [η] (measured in decalin at 135 ° C.) is 0.2 to 7 dl / g, preferably 0.5 to 5
It is desirable to produce a prepolymer of about dl / g.

In the present invention, ethylene is polymerized or ethylene and another olefin are copolymerized in the presence of the above solid catalyst or prepolymerization catalyst. 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 catalyst preparation can also be used. In the main polymerization, the amount of the solid catalyst or the pre-polymerization catalyst is transition metal / liter (polymerization volume), which is usually 10 ⁻⁸ to 10 ⁻³ g atom / liter, further 10 ⁻⁷ to 10 ⁻⁴ g atom / liter. It is desirable to be used in.

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)
It is possible to use 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

In the present invention, the main polymerization is usually -50 to 20.
0 ℃ preferably be at a temperature of 0 to 100 ° C., and usually, atmospheric pressure to 100 kg / cm ² preferably carried out under a pressure of normal 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] is produced by suspension polymerization, it is desirable to carry out at a polymerization temperature of 0 to 200 ° C., preferably 20 to 150 ° C., and solution polymerization is preferably 50 to 120 ° C. Is 60-1
It is desirable to carry out at a polymerization temperature of 10 ° 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. Further, in the present invention, when the ethylene-based polymer [A] is produced, the reaction conditions may be changed to carry out the polymerization in two or more stages.

The modifier for high-density polyethylene according to the present invention comprises the above-mentioned [A] ethylene-based polymer, and is particularly suitable as a modifier for mechanical strength, rigidity and moldability of high-density polyethylene for blow molding. is there.

Blow Molding Resin Composition A blow molding resin composition according to the present invention comprises an ethylene polymer [A] as described above and a blow molding high-density polyethylene [B] other than [A]. Consists of. As the high-density polyethylene [B], polyethylenes other than the ethylene-based polymer [A] produced by using the metallocene catalyst can be widely used, and high-density polyethylene known for blow molding can be widely used. Those manufactured by the high pressure method, those manufactured using a Ti-based catalyst or a Cr-based catalyst, and the like can be used. Among these, those produced using a titanium-based Ziegler catalyst are particularly preferably used. In the present invention, as the high-density polyethylene [B], specifically, (1) a unit derived from an α-olefin having 3 to 6 carbon atoms in an amount of less than 10 mol%, preferably 0 to 5 mol% is more preferable. May be contained in an amount of 0 to 3 mol%, and (2) the density is 0.94 to 0.98 g / cm ^3, preferably 0.95 to 0.97 g / cm ^3.
3 (3) The intrinsic viscosity [η] is 0.4 to 10 dl / g, preferably 0.5 to 8 dl / g, more preferably 1.0 to 5 dl / g, and (4) using a titanium-based Ziegler catalyst. It is preferable to use the produced ethylene polymer.

A blow molding resin composition comprising such an [A] ethylene-based polymer and a [B] high-density polyethylene, wherein [A] the ethylene-based polymer and [B]
The amount ratio of high-density polyethylene is [A]: [B] = 5-5
It is desirable that 0% by weight: 95 to 50% by weight, preferably 10 to 50% by weight: 90 to 50% by weight.

In the blow molding resin composition according to the present invention as described above, (1) the density is 0.94 to 0.98 g / cm ^3, preferably 0.9.
It is preferably 95 to 0.97 g / cm ³ . (2) It is desirable that the intrinsic viscosity [η] is 0.4 to 10 dl / g, preferably 0.5 to 8 dl / g, and more preferably 1.0 to 5.0 dl / g. (3) Melt flow rate (MFR) is 0.005-1
It is desirable that the amount is 0 g / 10 minutes, preferably 0.008 to 8 g / 10 minutes, and more preferably 0.01 to 5.0 g / 10 minutes.

(4) Melt tension (MT) is 1 to 1
It is desirable that the amount is 00 g, preferably 2 to 50 g. 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 (resin composition for blow molding) is used at a resin temperature of 190 using an MT measuring machine (manufactured by Toyo Seiki Seisakusho).
C, extrusion speed 15 mm / min, winding speed 10-20 m /
Min, the nozzle diameter is 2.09 mm and the nozzle length is 8 mm.

In such a blow molding resin composition according to the present invention, (5) the melt flow rate (MFR) value and the melt tension (MT) value are expressed by log [MT] ≧ −0.4 log [MFR ] +0.70 is preferable.

(6) Further, it is desirable that the blow molding resin composition satisfying such a relational expression has a diameter swell ratio of 1.35 or more, preferably 1.35 to 1.65. The blow molding resin composition having such a diameter swell ratio is excellent in moldability. When this blow molding resin composition is blow molded, a bottle having excellent pinch-off shape and excellent strength can be obtained. Bottle (hollow molded body)
Since it is possible to narrow the wall thickness distribution, the weight per unit area can be reduced, and if the weight per unit area is the same, a bottle excellent in buckling strength can be obtained.

The diameter swell ratio of the blow molding resin 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 is extruded at each piston speed of 0 and 75 (mm / min), and the strand diameter (D _i ) 15 mm below the nozzle outlet is measured by a laser beam. Strand diameter (D _i ) at each piston velocity measured in this way
To the tube nozzle diameter (D ₀ ) (SR _i = D _i / D
₀ ) is plotted for each piston velocity on a semilogarithmic graph paper, and the piston velocity 50 (mm / mi
The SR value at the time of n) is read and this SR value is used 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 blow molding resin composition of the present invention comprises:
Within the range that does not impair the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, and aging. It may contain an antioxidant, a hydrochloric acid absorbent, an antioxidant and the like.

The blow molding resin composition according to the present invention comprises:
The above-mentioned ethylene polymer [A] and high-density polyethylene [B] can be blended by a known method, or can be directly produced by polymerization as described above. As a blending method, (1) a method of blending the ethylene polymer [A], the high-density polyethylene [B] and, if desired, other components using an extruder, a kneader, or the like, (2) an ethylene polymer [A ], High density polyethylene [B] and optionally other components are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, xylene), and then the solvent is removed. Method (3) A method in which an ethylene polymer [A], a high-density polyethylene [B] and, if desired, other components are separately dissolved in a suitable good solvent to prepare a solution, which is then mixed, and then the solvent is removed. , (4) A method of performing a combination of the above methods (1) to (3).

The blow molding resin composition according to the present invention comprises:
It is excellent in blow moldability and can be blow molded by a conventionally known blow molding method. In this case, a blow molded product can be manufactured with high productivity. Further, the molded product molded in this manner is excellent in rigidity and mechanical strength. Such blow-molded article according to the present invention,
For example, it can be widely used as a chemical can, a drug can, a drum, a bottle, etc.
It is suitable as a large polyethylene can for chemicals of about 100 to 200 liters.

[0092]

EFFECT OF THE INVENTION The blow molding resin composition according to the present invention has excellent moldability and can produce a molded product having excellent mechanical strength and rigidity.

[0093]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
In the present invention, the physical properties of the blow molding resin composition were evaluated as follows. [Measurement of Melt Flow Rate MFR] ASTM D12
According to 38-65T, it was measured at 190 ° C. under a load of 2.16 kg. [Measurement of Melt Tension MT] The stretching stress was measured by the method described above. [Measurement of Diameter Swell Ratio] The diameter swell ratio was measured by the method described above.

[Izod impact strength] JIS K711
The test was performed according to 0. The test temperature was -30 ° C.

[0095]

[Production Example 1] Production of ethylene polymer [A] [Preparation of solid catalyst] 9.4 g of silica dried at 250 ° C. for 10 hours was suspended in 150 ml of toluene and then 0
Cooled to ° C. Then, a toluene solution of methylaluminoxane (Al; 1.594 mmol / ml) 45.3 m
1 was added dropwise over 40 minutes. At this time, the temperature in the system is 0 ℃
Kept at. Continue to react at 0 ° C for 30 minutes, then 30
The temperature was raised to 95 ° C over a period of time, and the reaction was performed 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 three times with toluene and then resuspended in 200 ml of toluene. Toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr; 0.00225)
(2.5 mmol / ml) (152.5 ml) was added at room temperature, and the mixture was further reacted at 80 ° C. for 2 hours. After that, the supernatant liquid was removed and washed with hexane three times to obtain 2.
A solid catalyst containing 1 mg of zirconium was obtained.

[Preparation of prepolymerization catalyst] 200 ml of hexane containing 4.0 mmol of triisobutylaluminum
To the solid catalyst 1 was added 3.5 g of the solid catalyst obtained above, and prepolymerization of ethylene was performed at 35 ° C. for 2 hours.
A prepolymerized catalyst in which 3 g of ethylene polymer was prepolymerized per g was obtained.

[Polymerization] A 2-liter autoclave was charged with 1 liter of hexane, and then 1.5 mmol of triisobutylaluminum and 0.01 mmol of the prepolymerized catalyst prepared above in terms of zirconium atom. Next, ethylene was continuously supplied, and the total pressure was 8 kg / cm ² G
Then, ethylene was polymerized at a polymerization temperature of 80 ° C.

445 g of ethylene polymer [A] (homopolyethylene) was obtained. The ethylene polymer has a density of 0.949 g / cm ³ and an intrinsic viscosity [η] of 2.4.
It is 9 dl / g and the melt flow rate (MFR) is 0.
It was 01 g / 10 minutes.

[0100]

Example 1 Production of Blow Molding Resin Composition 5 g of the ethylene polymer [A] obtained in Production Example 1 and high density polyethylene [B] produced using a titanium Ziegler catalyst (density = 0.955 g) / Cm ³ , [η] = 3.8 dl
/ G, MFR = 0.057 g / 10 min) 35 g, and phenol-based heat stabilizer (Irganox 1076, manufactured by Ciba-Geigy) 0.05 g, phosphorus-based heat stabilizer (Irgafos 168, manufactured by Ciba-Geigy)
After dry blending 0.025 g, using a batch type kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.),
It was melt-kneaded at 200 ° C. to obtain a blow molding resin composition. The density of the obtained blow molding resin composition was 0.95.
It was 4 g / cm ³ and the melt flow rate (MFR) was 0.04 g / 10 minutes. The results are shown in Table 1.

[0101]

Example 2 Production of Blow Molding Resin Composition A blow molding resin composition was obtained in the same manner as in Example 1 except that the amount of [A] was changed to 15 g.
The density of the obtained blow molding resin composition was 0.953 g.
/ Cm ³ and the MFR was 0.034 g / 10 minutes.
The results are shown in Table 1.

[0102]

[Comparative Example 1] High-density polyethylene [B] produced using a titanium-based Ziegler catalyst (density = 0.955 g / cm ³ ,
[[Eta]] = 3.8 dl / g, MFR = 0.057 g / 10 min) was used and tested in the same manner as in Example 1. The results are shown in Table 1.

[0103]

[Table 1]

As is clear from the above, the blow molding resin composition of the present invention is excellent in moldability, mechanical strength and rigidity.

[0105]

Example 3 Each of the blow molding resin compositions obtained in Examples 1 and 2 was blow molded into a 200 liter container using a blow molding machine with a resin temperature of 200 ° C., a die diameter of 230 mm and a 25 liter accumulator. I just did
A smooth blow-molded product with good molding stability and less uneven thickness unevenness was obtained.

[Brief description of drawings]

FIG. 1 shows an example of steps for producing an ethylene polymer [A].

Continued Front Page (72) Inventor Katsunori Yano 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (6)

[Claims] 1. [A] (1) It may contain units derived from an α-olefin having 3 to 6 carbon atoms in an amount of less than 10 mol%, and (2) the density is 0.92 to 0.9. 98 g / cm ³
And (3) the intrinsic viscosity [η] is 0.4 to 10 dl / g.
And (4) a modifier for high-density polyethylene, characterized by comprising an ethylene-based polymer produced using a catalyst containing a metallocene compound represented by the following general formula; (In the formula, M is a transition metal atom of groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom or 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 those groups in which some of the groups adjacent to each other are bound to each other. May form at least one ring with the carbon atom to which X is bonded, 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. , A halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a divalent silicon-containing group, a divalent germanium-containing group, or an alkylene group.). 2. A blow molding resin composition comprising [A] the ethylene polymer according to claim 1 and [B] a high density polyethylene for blow molding other than [A]. 3. The high-density polyethylene [B] contains 1 unit derived from (1) an α-olefin having 3 to 6 carbon atoms.
It is contained in an amount of less than 0 mol and (2) has a density of 0.94 to 0.9.
It is 98 g / cm ³ , (3) intrinsic viscosity [η] is 0.4 to 10 dl / g, and (4) is produced using a titanium-based Ziegler catalyst. The resin composition for blow molding according to item 1. 4. An ethylene-based polymer [A] and a high-density polyethylene [B] are contained in an amount ratio of [A]: [B] = 5 to 50% by weight: 95 to 50% by weight. The resin composition for blow molding according to claim 2 or 3. 5. In the blow molding resin composition, the melt flow rate (MFR) value and the melt tension (MT) value are expressed by the formula log [MT] ≧ −0.4 log [MFR] +0.7.
Satisfies the relationship indicated by 0 and has a radial swell (SR)
The blow molding resin composition according to any one of claims 2 to 4, wherein the ratio is 1.35 or more. 6. A blow-molded article obtained by blow-molding the resin composition for blow-molding according to claim 1.