JP2002080531A - Resin for polyethylene hollow molded article and polyethylene hollow molded article comprising the resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin having excellent extrusion characteristics on the production of a hollow molded article and capable of providing the polyethylene hollow molded article which has an appearance free from a scaly skin and has an excellent drop impact resistance, even when the resin is used in a smaller amount than the amount of a high density polyethylene used for its conventional hollow molded article. SOLUTION: This resin for the polyethylene hollow molded article in the first present invention is characterized by having a density of 920 to 940 kg/m3 and having an intrinsic viscosity [η] and MFR which satisfy the expressing: ([MFR]/10)-(1/1.8)>[η]>([MFR]/10)-(1/4.8). The resin for the polyethylene hollow molded article in the second present invention is characterized by comprising the high density polyethylene and a linear low density polyethylene in a specific ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for a polyethylene hollow molded article and a polyethylene hollow molded article comprising the resin.
The present invention relates to a resin for a polyethylene hollow molded article capable of preparing a polyethylene hollow molded article having no shark skin appearance, and a molded article thereof.

[0002]

2. Description of the Related Art Conventionally, hollow molded articles made of polyethylene, particularly high-density polyethylene, have been used for containers such as detergents, but their drop impact resistance is not always sufficient. Is desired. As a technique for improving the drop impact resistance of the hollow molded article, for example, there is a technique of increasing the molecular weight of high-density polyethylene or widening the molecular weight distribution (Mw / Mn).

However, all of these methods deteriorate the extrusion characteristics of high-density polyethylene and increase the resin pressure at the time of blow molding (blow molding). )
And the power consumption of the motor increases. Meanwhile, conventionally, it has been required to reduce the amount of resin used in a hollow molded article from the viewpoint of resource conservation and reduction of waste.

[0004] However, the density of the bottle, which is excellent in rigidity and drop impact resistance, is 930 kg / m ³ or more and 945 k
In the case of using a polyethylene material of g / m ³ or less, the conventional technology has a limitation in reducing the amount of resin used due to insufficient drop strength of the blow container. Therefore, a resin for a polyethylene hollow molded article comprising a high-density polyethylene composition capable of preparing a polyethylene hollow molded article having excellent extrusion characteristics and excellent drop impact resistance than before, and a polyethylene hollow molded article Appearance is desired.

Further, a polyethylene hollow molded article having excellent extrusion characteristics and capable of preparing a polyethylene hollow molded article having excellent drop impact resistance even with a smaller amount of resin than a conventional high-density polyethylene hollow molded article. Body resin,
In particular, the appearance of a resin comprising a high-density polyethylene composition and a polyethylene hollow molded article thereof are desired.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to perform blow molding (blow molding) using a high-density polyethylene composition having excellent extrusion characteristics. It is made of a high-density polyethylene composition that can be used to prepare a polyethylene hollow molded article that has excellent drop impact resistance and has no appearance of shark skin even with a smaller amount of resin used than a conventional high-density polyethylene hollow molded article. It is an object of the present invention to provide a resin for a polyethylene hollow molded article, and a polyethylene hollow molded article thereof.

Further, the present invention provides a hollow molded article (blow molding) using a high-density polyethylene composition having excellent extrusion characteristics, so that it is more excellent in drop impact resistance than a conventional high-density polyethylene hollow molded article, and An object of the present invention is to provide a resin for a polyethylene hollow molded article comprising a high-density polyethylene composition from which a polyethylene hollow molded article having no shark skin appearance can be prepared, and a polyethylene hollow molded article thereof.

[0008]

SUMMARY OF THE INVENTION The first resin for a polyethylene hollow molded article according to the present invention has a density (ASTM D1505) of 920 to 940 k.
g / m ³ , and the intrinsic viscosity [η] (unit: dl / g) measured in a decalin solvent at 135 ° C. is 1.6 <[η] <1.
0 and the melt flow rate (MF
R; ASTM D 1238, 190 ° C, 2.16 kg load, unit: g / 10
Min) and the intrinsic viscosity [η] (unit: dl / g) are ([MFR] / 10) ^{− (1 / 1.8)} >[η]> ([MFR]
/ 10) It is characterized by being a polyethylene satisfying the formula ^{of-(1 / 4.8)} .

As the polyethylene, ASTM D
The melt flow rate (MFR _21.6 ) measured under a load of _21.6 kg according to 1238 (190 ° C.)
Melt flow rate (MFR) measured at a load of 16 kg
_2.16 ) divided by the value [(MFR _21.6 ) / (MFF
R _2.16 )] is more than 30.
The polyethylene has a density (ASTM D 1505) of 9
It is prepared using a high-density polyethylene (A) having an intrinsic viscosity [η] of 1.5 to 5 dl / g measured in a decalin solvent at 135 ° C. and a catalyst for metallocene olefin polymerization, which is 40 kg / m ³ or more. And density (ASTM D 150
5) is less than 920 kg / m ³ , and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.0 to 10 dl / g.
And a linear low-density polyethylene (B), wherein the content of the linear low-density polyethylene (B) in the polyethylene composition is higher than that of the high-density polyethylene (A). The polyethylene composition is preferably used in an amount of 2 to 30 parts by weight based on 100 parts by weight in total with the low-density polyethylene (B).

G of the linear low-density polyethylene (B)
The molecular weight distribution (Mw / Mn) measured by PC is usually 2 to 5, preferably 2.5 to 4.0. The linear low-density polyethylene (B) has a normal-temperature n-decane-soluble component fraction (W) of usually 0 to 15% by weight, preferably 0 to 10% by weight. The polyethylene composition may have 0
A single-layer bottle with a drop height of 1.8 m or more (internal capacity: 780 ml, tare weight: 25 g) that does not allow the water filled in the bottle to leak to the outside in five repeated drop tests in an atmosphere at a temperature of ℃. Is possible.

The first polyethylene hollow molded article according to the present invention is characterized in that it has a layer made of the resin for the first polyethylene hollow molded article according to the present invention as described above. When the polyethylene hollow molded body is a container,
It is desirable that the average container weight per 100 cc of the tare is 4 g or less.

The first hollow polyethylene molded article according to the present invention may be a multilayer container. The first hollow molded article according to the present invention is suitably used as a container for a surfactant or a container for a bleaching agent. The resin for the first polyethylene hollow molded article according to the present invention, in particular, the polyethylene composition containing the specific high-density polyethylene (A) and the specific linear low-density polyethylene (B) at a specific ratio is used for the hollow molding. Extruding characteristics or blow moldability.

The first hollow polyethylene molded article according to the present invention has an appearance free of shark skin, and has excellent drop impact resistance even when the amount of resin used is smaller than that of a conventional high-density polyethylene hollow molded article. ing. The second resin for a polyethylene hollow molded article according to the present invention has a density (ASTM D 1505) of 9
It is prepared using a high-density polyethylene (A) having an intrinsic viscosity [η] of 1.5 to 5 dl / g measured in a decalin solvent at 135 ° C. and a catalyst for metallocene olefin polymerization, which is 40 kg / m ³ or more. And density (ASTM D 150
5) is less than 920 kg / m ³ , and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.0 to 10 dl / g.
And a linear low-density polyethylene (B), wherein the content of the linear low-density polyethylene (B) in the polyethylene composition is higher than that of the high-density polyethylene (A). 2 to 30 parts by weight with respect to 100 parts by weight in total with the low-density polyethylene (B).

G of the linear low density polyethylene (B)
The molecular weight distribution (Mw / Mn) measured by PC is usually 2 to 5, preferably 2.5 to 4.0. The linear low-density polyethylene (B) has a normal-temperature n-decane-soluble component fraction (W) of usually 0 to 15% by weight, preferably 0 to 10% by weight. The high-density polyethylene (A)
135 of a mixture of ethylene and linear low density polyethylene (B)
The intrinsic viscosity [η] measured in decalin solvent at 1.3 ° C. is 1.3.
10 to 10 dl / g, preferably 1.8 to 5 dl / g, and a density (ASTM D 1505) of 890 to 962 kg.
/ M ³ , preferably 920 to 940 kg / m ³ .

[0015] The polyethylene composition is a single-layer bottle (having a capacity of 780 ml) whose drop height is not less than 1.8 m so that water filled in the bottle does not leak outside in a repeated drop test five times in an atmosphere of 0 ° C. , A tare weight of 25 g) can be hollow-formed. The second polyethylene hollow molded article according to the present invention is characterized in that it has a layer made of the resin for the second polyethylene hollow molded article according to the present invention as described above.

The second polyethylene hollow molded article according to the present invention may be a multilayer container. The second hollow molded article according to the present invention is suitably used as a container for a surfactant or a container for a bleaching agent. The second resin for a polyethylene hollow molded article according to the present invention is a specific high-density polyethylene (A).
In addition, since a specific linear low-density polyethylene (B) is blended in a specific ratio, the extrusion characteristics or blow moldability during hollow molding are excellent.

The second polyethylene hollow molded article according to the present invention has an appearance free of shark skin, and is more excellent in drop impact resistance than the conventional high-density polyethylene hollow molded article.

[0018]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the resin for a polyethylene hollow molded article according to the present invention and the polyethylene hollow molded article using the resin will be described in detail. The first resin for a polyethylene hollow molded article according to the present invention has a specific density and intrinsic viscosity [η], and has a melt flow rate (M
FR) and intrinsic viscosity [η] are polyethylene having a specific relationship. As the polyethylene, a specific polyethylene composition containing a high-density polyethylene (A) and a linear low-density polyethylene (B) is used. It is preferably used.
The first polyethylene hollow molded article according to the present invention has the above-mentioned layer made of the first resin according to the present invention.

The second resin for a polyethylene hollow molded article according to the present invention is a polyethylene composition containing a high-density polyethylene (A) and a linear low-density polyethylene (B). The second hollow polyethylene molded article according to the present invention has the above-mentioned layer made of the second resin according to the present invention. The high-density polyethylene (A) and the linear low-density polyethylene (B) constituting the resin for the first polyethylene hollow molded article according to the present invention are respectively used for the second polyethylene hollow molded article according to the present invention. It is the same as the high-density polyethylene (A) and the linear low-density polyethylene (B) constituting the resin.

High Density Polyethylene (A) The polyethylene composition preferably used as the resin for the first polyethylene hollow molded article according to the present invention and the polyethylene composition as the second resin for the polyethylene hollow molded article according to the present invention Constituting high density polyethylene (A)
Has a density of 940 kg / m ³ or more, usually 940 to 970
kg / m ^3, preferably not 940~960kg / m ^3, more preferably a 940~950kg / m ^3.

Further, this high-density polyethylene (A)
The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.5 to 5 dl / g, preferably 1.8 to 5 dl / g. When the intrinsic viscosity of the high-density polyethylene (A) is within the above range, a polyethylene composition having excellent extrusion characteristics during blow molding (blow molding) can be obtained. The high-density polyethylene (A) used in the present invention may be a high-density polyethylene having the above-mentioned density and intrinsic viscosity. Not only ethylene homopolymer but also ethylene and a small amount of α-olefin, for example, 10 mol % Propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-
Α- such as methyl-1-pentene and 4-methyl-1-pentene
An ethylene / α-olefin copolymer obtained by copolymerizing an olefin can also be used.

High density polyethylene (A) as described above
Can be prepared by a conventionally known method. In the present invention, the high-density polyethylene (A) is used in an amount of 70 to 98 parts by weight, preferably 75 to 98 parts by weight, based on 100 parts by weight of the total of the high-density polyethylene (A) and the linear low-density polyethylene (B). 95 parts by weight, more preferably 78 to 8
Used in a proportion of 5 parts by weight.

Linear low-density polyethylene (B) A polyethylene composition preferably used as the resin for the first polyethylene hollow molded article according to the present invention, and polyethylene as the resin for the second polyethylene hollow molded article according to the present invention The linear low-density polyethylene (B) constituting the composition is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a metallocene olefin polymerization catalyst. -It is an olefin copolymer.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, Hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,
3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, trimethyl-1-butene,
Ethyl-1-pentene, 1-octene, methyl-1-pentene, dimethyl-1-hexene, trimethyl-1-pentene,
Ethyl-1-hexene, methylethyl-1-pentene, diethyl-1-butene, propyl-1-pentene, 1-decene, methyl-1-nonene, dimethyl-1-octene, trimethyl-1
-Heptene, ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene, 1-hexadedecene and the like.

These α-olefins can be used alone or in combination of two or more. Linear low density polyethylene (B) preferably used in the present invention
Are ethylene-propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene・ It is a 1-octene copolymer.

The linear low-density polyethylene (B) has a constitutional unit derived from ethylene of usually 65 to 99% by weight, preferably 70 to 98% by weight, more preferably 75 to 9% by weight.
A structural unit derived from an α-olefin having 3 to 20 carbon atoms, which is present in an amount of 6% by weight, usually 1 to 35% by weight;
Preferably 2 to 30% by weight, more preferably 4 to 25%
It is present in an amount of% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by ¹³ C-NMR of a sample in which about 200 mg of the ethylene / α-olefin copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a sample tube of 10 mmφ. The spectrum was measured at a measurement temperature of 120 ° C. and a measurement frequency of 25.05 MH.
z, spectral width 1500 Hz, pulse repetition time4.
It is determined by measuring under conditions of 2 sec. And pulse width of 6 μsec.

The density (ASTM D 1505) of the linear low density polyethylene (B) is less than 920 kg / m ³ , usually 850
kg / m ³ or more and less than 920 kg / m ³ , preferably 860
915 kg / m ³ , more preferably 895-910
kg / m ³ . When the linear low-density polyethylene (B) having a density within the above range is used, a polyethylene composition capable of providing a hollow molded article having excellent drop impact resistance is obtained.

Further, linear low density polyethylene (B)
Is the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C.
Is 1.0 to 10 dl / g, preferably 1.3 to 4.5 d
1 / g, more preferably 1.5 to 2.5 dl / g. When a linear low-density polyethylene (B) having an intrinsic viscosity within the above range is used, the obtained polyethylene composition provides a hollow molded article having excellent extrusion characteristics at the time of hollow molding and having an appearance without shark skin. Can be.

Further, linear low density polyethylene (B)
The normal-temperature n-decane-soluble component fraction (W) is usually 0 to 15
% By weight, preferably in the range of 0 to 10% by weight. The measurement of the normal temperature n-decane soluble component amount fraction (W) is performed by adding about 3 g of linear low-density polyethylene to 450 ml of n-decane,
After dissolving at 145 ° C., the mixture is cooled to 23 ° C., the n-decane insoluble portion is removed by filtration, and the n-decane soluble portion is recovered from the filtrate to carry out.

The n-decane soluble component fraction (W) is defined by the following equation. W [%] = (weight of n-decane-soluble portion / total weight of n-decane-insoluble portion and soluble portion) × 100 The smaller the n-decane-soluble component amount fraction, the lower the linear low density. Meaning that the composition distribution of polyethylene is narrow, and when this n-decane-soluble component amount fraction is within the above range, the low-molecular-weight component causing stickiness is very small, and a hollow molded article excellent in printability. Is obtained.

In the present invention, if a linear low-density polyethylene prepared using a conventionally known Ziegler-based olefin polymerization catalyst is used instead of the linear low-density polyethylene (B), Low-density polyethylene has many sticky components, so the obtained hollow molded body is
The printability is inferior to the polyethylene hollow molded article according to the present invention, and the drop impact resistance is also insufficient.

The linear low-density polyethylene (B) has a molecular weight distribution (Mw / M) measured by gel permeation chromatography (GPC).
n: Mw = weight average molecular weight, Mn = number average molecular weight)) is usually in the range of 2 to 5, preferably 2.5 to 4.0. When a linear low-density polyethylene (B) having a molecular weight distribution within the above range is used, a hollow molded article with less stickiness can be prepared.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore. The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., and the mobile phase was o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and antioxidant B as an agent
Using HT (manufactured by Takeda Pharmaceutical Co., Ltd.) 0.025% by weight, moving at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and the differential detector was used. A refractometer was used. Standard polystyrene is
For a molecular weight of Mw <1000 and Mw> 4 × 10 ⁶ , use Tosoh Corporation and 1000 ≦ Mw ≦ 4 × 10 6
About ⁶ , the product made by Pressure Chemical Company was used.

The linear low-density polyethylene (B) is a metallocene-based olefin polymerization catalyst such as a transition metal compound (a) belonging to Group IV of the periodic table containing a cyclopentadienyl skeleton, an organic aluminum oxy compound. (B) in the presence of an olefin polymerization catalyst formed from a support (c), optionally an organoaluminum compound (d),
It can be prepared by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.

The olefin polymerization catalyst and each catalyst component will be described below. Transition metal compound (a) The transition metal compound (a) belonging to Group IV of the periodic table containing a cyclopentadienyl skeleton is specifically a transition metal compound represented by the following formula (I). ML ¹ _X (I) (wherein M represents a transition metal selected from Group IV of the periodic table, L ¹ represents a ligand coordinated to a transition metal atom,
At least two of the ligands L ¹ are preferably a cyclopentadienyl group, particularly a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, The ligand L ¹ other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom,
X is a trialkylsilyl group or a hydrogen atom, and X represents the valence of the transition metal atom M. Examples of the transition metal compound (a) represented by the general formula (I) include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride, and bis (methylethylcyclopentadiene). (Enyl) zirconium dichloride, bis (dimethylethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis (dimethylcyclopentadienyl) zirconium methoxychloride, bis (dimethylcyclopentadienyl) zirconium Ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium diethoxide, bis (dimethylcyclopentadiene) B) zirconium methyl chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium Phenyl chloride, bis (dimethylcyclopentadienyl) zirconium hydride chloride and the like can be mentioned.

In the above examples, disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted, and trisubstituted 1,2-, 3- and 1,2,4- Including substitutions. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the zirconium compound as described above can be used. Among these transition metal compounds represented by the general formula (I),
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride, bis (1 -Methyl-3-n-butylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride are particularly preferred.

The transition metal compound (a) used in the present invention
Is a transition metal compound represented by the general formula (I);
It may be a mixture with a transition metal compound represented by the following general formula (II). Further, the transition metal compound represented by the general formula (II) can be used alone. MKL ² _X-2 (II) (wherein, M represents a transition metal atom selected from Group IVB of the periodic table, and K and L ² represent ligands coordinated to the transition metal atom. The ligand K is a bidentate ligand in which the same or different indenyl group, substituted indenyl group or a partial water additive thereof is bonded via a lower alkylene group, and the ligand L ² is a carbon atom. A hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom of the formulas 1 to 12, and X represents a transition metal atom M
The valence of As the transition metal compound represented by the general formula (II), specifically, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4-methyl-1-indenyl) zirconium dichloride, ethylene bis (4, Five,
6,7-tetrahydro-1-indenyl) zirconium dichloride.

At least one transition metal compound (a) selected from the transition metal compounds represented by the general formula (I)
-1) and at least one transition metal compound selected from the transition metal compounds represented by the general formula (II) (a-
2) means 99/1 to 50 / in molar ratio ((a-1) / (a-2)).
50, preferably 97/3 to 70/30, more preferably 95/5 to 75/25, most preferably 90/10
It is desirable to use an amount such that it is in the range of 80/20.

Organic Aluminum Oxy Compound (b) The organic aluminum oxy compound (b) used in the present invention includes, for example, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and the like. A conventionally known benzene-soluble aluminoxane may be used.
Or a benzene-insoluble organic aluminum oxy compound as disclosed in Japanese Patent Application Publication No.

Carrier (c) The carrier (c) used in the present invention is an inorganic or organic compound, and is a granular or fine solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm. You. For example, as the inorganic carrier, a porous oxide is preferable, and particularly, a carrier mainly containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ is preferably used.

The carrier (c) has different properties depending on the kind and the manufacturing method. The carrier (c) preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. Yes, pore volume is 0.3
It is desirably about 2.5 cm ³ / g. The carrier (c) is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, as the case requires.

Organoaluminum compound (d) Examples of the optionally used organoaluminum compound (d) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, trioctylaluminum and trioctylaluminum.
Trialkyl aluminum such as 2-ethylhexyl aluminum; alkenyl aluminum; dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; alkyl aluminum sesquihalide; alkyl aluminum dihalide; alkyl aluminum Hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and diisobutylaluminum methoxide.

An organic boron compound can be used in place of the organic aluminum compound. When the transition metal compound (a), the organoaluminum oxy compound (b), the carrier (c) and optionally the organoaluminum compound (d) are mixed and contacted, the transition metal compound (a) is usually added per 1 g of the carrier (c). 5 × 10 ^-6 ~5 × 10 ^-4 mol, preferably used in an amount of 10 ^-5 ~2 × 10 ^-4 mol, the concentration of the transition metal compound (a) is about 10 ^-4 ~2 × 10 ^{- The range is 2} mol / l, preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / l. The atomic ratio (Al / transition metal) of aluminum of the organoaluminum oxy compound (b) to the transition metal in the transition metal compound (a) is usually 10 to 50.
0, preferably 20 to 200. The aluminum atom (A) of the optionally used organoaluminum compound (d)
Atomic ratio (Al-d / Al-b) between l-d) and aluminum atom (Al-b) of the organoaluminum oxy compound (b)
Is usually 0.02 to 3, preferably 0.05 to 1.5
Range.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in a gas phase or in a liquid phase in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent. When the polymerization is carried out by a slurry polymerization method or a gas phase polymerization method, the olefin polymerization catalyst as described above generally has a transition metal atom concentration of 10 ^-8 to 10 ^-3 g atom / liter, preferably 10 ^-10 g atom / liter, in the polymerization reaction system. ^Preferably, it is used in an amount of ^-7 to 10 ^-4 gram atoms / liter.

When performing the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. When performing the gas phase polymerization method, the polymerization temperature is: Usually, it is in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably under a pressurized condition of ^{2 to} 50 kg / cm ² , and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

Further, the polymerization can be carried out in two or more stages having different reaction conditions, and the polymerization reaction can be accelerated in a single stage or in multiple stages including preliminary polymerization. In the present invention, the linear low-density polyethylene (B) is preferably 2 to 30 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the total of the high-density polyethylene (A) and the linear low-density polyethylene (B). Is used in a proportion of 5 to 25 parts by weight, more preferably 15 to 22 parts by weight. When the linear low-density polyethylene (B) prepared using the metallocene-based olefin polymerization catalyst is used at a ratio within the above range, the resulting polyethylene composition has excellent extrusion characteristics during hollow molding,
It is possible to provide a polyethylene hollow molded article having an appearance without shark skin and having excellent drop impact resistance.

Polyethylene Composition The polyethylene composition preferably used as the first resin for a polyethylene hollow molded article according to the present invention comprises the above-described high-density polyethylene (A) and linear low-density polyethylene (B). It has a specific ratio as described above, has a density (ASTM D1505) of 920 to 940 kg / m ³ , preferably 925 to 935 kg / m ³ , and has an intrinsic viscosity [η] (unit: dl / g)
Is in the range of 1.6 <[η] <10, preferably 1.6 <[η] <5, and more preferably 1.8 <[η] <3.

The polyethylene composition has a melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load, unit: g / 10 minutes) and the intrinsic viscosity [η] (unit:
dl / g) is obtained by ([MFR] / 10) ^{-(1 / 1.8)} >[η]> ([MFR]
/ 10) ^-The formula ^{of-(1 / 4.8)} is satisfied.

By using a polyethylene composition having an intrinsic viscosity [η] within the above range and satisfying the above-mentioned relational expression between the MFR and the intrinsic viscosity [η], a polyethylene hollow molded container, for example, 100 cc Even if the average container weight is 4 g or less, sufficient drop strength can be obtained. In addition, a container excellent in appearance without shark skin can be obtained.

The polyethylene composition was prepared according to ASTM D
The melt flow rate (MFR _21.6 ) measured under a load of _21.6 kg according to 1238 (190 ° C.)
Melt flow rate (MFR) measured at a load of 16 kg
_2.16 ) divided by the value [(MFR _21.6 ) / (MFF
R _2.16 )] is more than 30. When a polyethylene composition having this value exceeding 30 is used, a hollow molded article such as a bottle excellent in appearance without shark skin can be obtained.

As described above, the second resin for a polyethylene hollow molded article according to the present invention is a polyethylene composition containing a high-density polyethylene (A) and a linear low-density polyethylene (B). High density polyethylene (A)
135 of a mixture of ethylene and linear low density polyethylene (B)
The intrinsic viscosity [η] measured in decalin solvent at 1.3 ° C. is 1.3.
10 to 10 dl / g, preferably 1.8 to 5 dl / g, and a density (ASTM D 1505) of 890 to 962 kg.
/ M ³ , preferably 920 to 940 kg / m ³ .

The polyethylene composition which is preferably used as the resin for the first polyethylene hollow molded article according to the present invention and the polyethylene composition which is the resin for the second polyethylene hollow molded article according to the present invention are prepared at 0 ° C. in an atmosphere. It is possible to blow-mold a single-layer bottle (internal capacity: 780 ml, tare weight: 25 g) with a drop height of 1.8 m or more, at which the water filled in the bottle does not leak to the outside in the five repeated drop tests. . In this drop test, if the bottle is repeatedly dropped on the floor five times vertically from the same height and the water in the bottle does not leak outside from the bottle, the drop test at that height is considered to be passed.

The above polyethylene composition can be prepared, for example, by melt-kneading the above-described high-density polyethylene (A) and linear low-density polyethylene (B) at a specific ratio. The kneading can be performed using a kneading device such as a single-screw extruder, a twin-screw extruder, a twin-screw kneader, a Banbury mixer, and a roll.

To produce this composition, the above-mentioned components are made uniform by applying the mixing method used in the field of ordinary polyethylene compositions so as to have the above-mentioned specific composition ratio. Just mix them. In addition, various additives can be added to the polyethylene composition as long as the physical properties of the hollow molded article are not impaired.

As such additives, specifically,
Fillers, weather stabilizers, heat stabilizers, antistatic agents, anti-slip agents, anti-fog agents, lubricants, pigments, dyes, nucleating agents, plasticizers,
Flame retardants, hydrochloric acid absorbents and the like can be mentioned. The polyethylene composition obtained as described above has a specific high-density polyethylene (A) mixed with a specific linear low-density polyethylene (B) at a specific ratio. Excellent blow moldability.

Polyethylene hollow molded article The first preferred polyethylene hollow molded article according to the present invention,
And the second polyethylene hollow molded body according to the present invention,
It consists of a polyethylene composition as described above. The first polyethylene hollow molded article according to the present invention preferably has an average weight of 4 g or less, usually 2 to 4 g per 100 cc of polyethylene hollow molded article (tare) from the viewpoint of resource conservation and waste reduction.

The first and second polyethylene hollow molded articles according to the present invention may be formed in a single layer as in a single-layer container, or may be formed in two or more layers as in a multilayer container. May be. For example, when the multilayer container is formed of two layers, one layer is formed of the polyethylene composition preferably used in the present invention described above, and the other layer is formed of a resin different from the polyethylene composition forming one layer. Or a polyethylene composition preferably used in the present invention described above and having physical properties different from those of the polyethylene composition used in one layer.

Examples of the different resin include polyamide (nylon 6, nylon 66 nylon 12, copolymerized nylon, etc.), ethylene / vinyl alcohol copolymer, polyethylene terephthalate, modified polyolefin and the like. The first and second polyethylene hollow molded articles according to the present invention are prepared by a conventionally known hollow molding (blow molding) method. The blow molding method includes various methods, and is roughly classified into an extrusion blow molding method, a two-stage blow molding method, and an injection molding method. In the present invention, an extrusion blow molding method is particularly preferably employed.

The hollow molded article prepared as described above is particularly suitable for uses such as a surfactant container or a bleaching container which requires a beautiful appearance without shark skin, such as cosmetics, detergents and softening agents. It can be suitably used as a container for a surfactant or a container for a bleach for home use and business use used in shampoos, rinses, treatments and the like.

[0061]

The first resin for a polyethylene hollow molded article according to the present invention has a density (ASTM D 1505) of 920 to 940.
kg / m ³ , and the intrinsic viscosity [η] (unit: dl / g) measured in a decalin solvent at 135 ° C. is 1.6 <[η] <
10 and MFR (ASTM D 1238,190
° C, 2.16 kg load, unit: g / 10 min) and the intrinsic viscosity [η] (unit: dl / g) are ([MFR] / 10)
^{-(1 / 1.8)} >[η]> ([MFR] / 10)-Made of polyethylene satisfying the formula of ^{(1 / 4.8)} , it is excellent in extrusion characteristics or blow moldability during hollow molding.

Since the first polyethylene hollow molded article according to the present invention is molded from the above-mentioned resin for the first polyethylene hollow molded article according to the present invention, it has an appearance free of shark skin and a conventional polyethylene hollow molded article. Even if the amount of resin used is smaller than that of the hollow molded body made of high-density polyethylene, it is excellent in drop impact resistance. This hollow molded article is excellent in printability. The second resin for a polyethylene hollow molded article according to the present invention is a polyethylene composition comprising a specific high-density polyethylene (A) and a specific linear low-density polyethylene (B) in a specific ratio. Therefore, it is excellent in extrusion characteristics or blow moldability during hollow molding.

Since the second polyethylene hollow molded article according to the present invention is molded from the above-mentioned resin for the second polyethylene hollow molded article according to the present invention, it has an appearance free of shark skin and a conventional polyethylene hollow molded article. It has better drop impact resistance than hollow molded articles made of high-density polyethylene. Further, this hollow molded body is excellent in printability. The resin for the first and second polyethylene hollow molded articles according to the present invention and the first and second polyethylene hollow molded articles according to the present invention include a detergent,
Shampoo, rinse, bleach, softener, cosmetics,
Containers for wax, edible oil, mayonnaise, and wasabi
It can be suitably used for applications such as gasoline tanks, chemical cans, drums, and water tanks.

[0064]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. (Examples and Comparative Examples of First Resin for Polyethylene Hollow Molded Article According to the Present Invention and Hollow Molded Article Made of the Resin) Polyethylene used in Examples and Comparative Examples is as follows. High-density polyethylene (1) HDPE (1) Density (ASTM D 1505) = 942 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 2.4 d
1 / g (2) HDPE (2) Density (ASTM D 1505) = 942 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 1.8 d
1 / g (3) HDPE (3) Density (ASTM D 1505) = 942 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 1.5 d
1 / g Linear low-density polyethylene (1) M-LLDPE (1) Catalyst used in the preparation: Catalyst for metallocene olefin polymerization Density (ASTM D 1505) = 902 kg / m ³ Intrinsic viscosity (135 ° C decalin solvent) = 1.7d
1 / g Mw / Mn = 2.2 Room temperature n-decane soluble component content rate (W) = 5% by weight (2) M-LLDPE (2) Catalyst used in the preparation: Catalyst for metallocene olefin polymerization Density (ASTM D 1505) = 902 kg / m ³ intrinsic viscosity (measured in decalin solvent at 135 ° C.) = 1.0 d
1 / g Mw / Mn = 2.3 Room temperature n-decane soluble component content (W) = 5% by weight (3) T-LLDPE (1) Catalyst used in the preparation: Ziegler-based olefin polymerization catalyst Density (ASTM D 1505) = 905 kg / m ³ Intrinsic viscosity (measured at 135 ° C. in decalin solvent) = 0.8 d
1 / g Mw / Mn = 2.8 Room temperature n-decane soluble component content rate (W) = 20% by weight

[0065]

Example A1 First, 80 parts by weight of HDPE (1) and 20 parts by weight of M-LLDPE (1) were melt-kneaded at 210 ° C. using a single screw extruder to prepare a polyethylene composition. The obtained polyethylene composition had an intrinsic viscosity of 2.20 dl / g and a density (ASTM D 1505) of 931 kg / m ³ measured in a decalin solvent at 135 ° C.

Next, this polyethylene composition was subjected to an extrusion blow molding machine (manufactured by Nippon Steel Corporation, model number: JEB-1).
Using 5), blow molding is performed under the following molding conditions, and the content is 7
A bottle (single-layer hollow molded body) weighing 80 ml and weighing 25 g was obtained. <Blow molding conditions> Molding temperature of polyethylene composition (resin): 200 ° C Resin pressure: 300 kg / m ² Resin extrusion rate: 50 kg / hr Mold temperature: 20 ° C The bottle obtained as described above is repeatedly dropped. The test was performed according to the following method. The result is
Shown in the table. <Test method> A single-layer bottle having a capacity of 780 ml and a weight of 25 g was filled with water, and the bottle was vertically set to drop vertically five times at a constant temperature of 0 ° C. The drop test was repeated five times. The maximum drop height at which water did not leak from the bottle to the outside was measured, and this maximum drop height was used as an index of the drop impact resistance of the bottle. Thickness 2 on the floor where the bottles fall
A steel plate having a thickness of not less than mm was placed horizontally on a concrete floor.

The bottle obtained did not have shark skin.

[0068]

Comparative Example A1 In Example A1, the HDPE (1) 100 was replaced with the polyethylene composition of Example A1.
Parts by weight were used. This polyethylene has an intrinsic viscosity of 2.4 dl / g measured in a decalin solvent at 135 ° C.,
The density (ASTM D 1505) was 942 kg / m ³ .

Next, this polyethylene composition was blow-molded using an extrusion blow-molding machine under the same molding conditions as in Example A1, to obtain a bottle (single-layer hollow molded body) having an internal capacity of 780 ml and a weight of 25 g. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 1 shows the results.

The obtained bottle had no shark skin.

[0071]

Comparative Example A2 The procedure of Example A1 was repeated except that 70 parts by weight of the HDPE (3) and 30 parts by weight of the T-LLDPE (1) were used instead of the polyethylene composition of Example A1. Similarly, a polyethylene composition was prepared. The resulting polyethylene composition was 135
1.30 dl / intrinsic viscosity measured in decalin solvent
g and a density (ASTM D 1505) of 932 kg / m ³ .

Next, this polyethylene composition was blow-molded using an extrusion blow-molding machine under the same molding conditions as in Example A1, to obtain a bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 1 shows the results.

The obtained bottle had no shark skin.

[0074]

Comparative Example A3 The procedure of Example A1 was repeated except that the polyethylene composition of Example A1 was replaced by 80 parts by weight of the HDPE (2) and 20 parts by weight of the T-LLDPE (1). Similarly, a polyethylene composition was prepared. The resulting polyethylene composition was 135
The intrinsic viscosity measured in a decalin solvent at 1.60 ° C. is 1.60 dl /
g and a density (ASTM D 1505) of 932 kg / m ³ .

Next, this polyethylene composition was blow-molded using an extrusion blow-molding machine under the same molding conditions as in Example A1 to obtain a bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 1 shows the results.

The obtained bottle had shark skin.

[0077]

Example A2 The procedure of Example A1 was repeated except that the polyethylene composition of Example A1 was replaced by 80 parts by weight of the HDPE (2) and 20 parts by weight of the M-LLDPE (2). Similarly, a polyethylene composition was prepared. The resulting polyethylene composition was 135
The limiting viscosity measured in decalin solvent at 1.65 dl /
g and a density (ASTM D 1505) of 932 kg / m ³ .

Next, the polyethylene composition was blow-molded using an extrusion blow-molding machine under the same molding conditions as in Example A1, to obtain a bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g. The bottle thus obtained was repeatedly subjected to a drop test according to the above method. Table 1 shows the results.

The obtained bottle had no shark skin.

[0080]

[Table 1]

(Examples and Comparative Examples of the Second Resin for Polyethylene Hollow Molded Article and the Hollow Molded Article Made of the Resin) Polyethylene used in Examples and Comparative Examples is as follows. High-density polyethylene (1) HDPE (4) Density (ASTM D 1505) = 961 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 2.0 d
1 / g (2) HDPE (5) Density (ASTM D 1505) = 955 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 2.2 d
1 / g (3) HDPE (6) Density (ASTM D 1505) = 948 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C) = 2.2 d
1 / g Linear low-density polyethylene (1) M-LLDPE (3) Catalyst used in the preparation: Catalyst for metallocene olefin polymerization Density (ASTM D 1505) = 902 kg / m ³ Intrinsic viscosity (135 ° C decalin solvent) Measured in) = 1.80
dl / g Mw / Mn = 2.5 Room temperature n-decane soluble component content ratio (W) = 7.0% by weight (2) M-LLDPE (4) Catalyst used in preparation: Metallocene olefin polymerization Catalyst density (ASTM D 1505) = 912 kg / m ³ Intrinsic viscosity (measured in decalin solvent at 135 ° C.) = 1.40
dl / g Mw / Mn = 2.3 Room temperature n-decane soluble component content rate (W) = 1.5% by weight (3) M-LLDPE (5) Catalyst used in the preparation: For metallocene olefin polymerization Catalyst density (ASTM D 1505) = 930 kg / m ³ intrinsic viscosity (measured in decalin solvent at 135 ° C.) = 1.70
dl / g Mw / Mn = 2.5 Room temperature n-decane soluble component content (W) = 0.5% by weight (4) T-LLDPE (2) Catalyst used in the preparation: for Ziegler-based olefin polymerization Catalyst density (ASTM D 1505) = 902 kg / m ³ Intrinsic viscosity (measured at 135 ° C. in decalin solvent) = 1.60
dl / g Mw / Mn = 3.0 Room temperature n-decane soluble component content ratio (W) = 17% by weight

[0082]

Example B1 First, 90 parts by weight of the above HDPE (4) and 10 parts by weight of M-LLDPE (3) were melt-kneaded at 210 ° C. using a single screw extruder to prepare a polyethylene composition. The resulting polyethylene composition had an intrinsic viscosity of 2.00 dl / g and a density (ASTM D 1505) of 955 kg / m ³ measured in a decalin solvent at 135 ° C.

Next, this polyethylene composition was subjected to an extrusion blow molding machine (manufactured by Nippon Steel Corporation, model number: JEB-1).
Using 5), blow molding is performed under the following molding conditions, and the content is 7
A bottle (single-layer hollow molded body) weighing 80 ml and weighing 25 g was obtained. <Blow molding conditions> Molding temperature of polyethylene composition (resin): 200 ° C Resin pressure: 300 kg / m ² Resin extrusion rate: 50 kg / hr Mold temperature: 20 ° C The bottle obtained as described above is repeatedly dropped. The test was performed according to the following method. The result is
Shown in the table. <Test method> A single-layer bottle having a capacity of 780 ml and a weight of 25 g was filled with water, and the bottle was vertically set to drop vertically five times at a constant temperature of 0 ° C. The drop test was repeated five times. The maximum drop height at which water did not leak from the bottle to the outside was measured, and this maximum drop height was used as an index of the drop impact resistance of the bottle. Thickness 2 on the floor where the bottles fall
A steel plate having a thickness of not less than mm was placed horizontally on a concrete floor.

The obtained bottle had no shark skin and good appearance.

[0085]

Example B2 In Example B1, the mixing amounts of HDPE (4) and M-LLDPE (3) were each 80 parts by weight,
A polyethylene composition was prepared in the same manner as in Example B1, except that the composition was changed to 20 parts by weight. The resulting polyethylene composition has an intrinsic viscosity of 1.90 dl / g measured in a decalin solvent at 135 ° C. and a density (ASTM D 1505).
Was 948 kg / m ³ .

Next, the polyethylene composition was blow-molded using an extrusion blow molding machine under the following molding conditions.
A bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g was obtained. <Blow molding conditions> Molding temperature of polyethylene composition (resin): 200 ° C Resin pressure: 280 kg / m ² Resin extrusion rate: 50 kg / hr Mold temperature: 20 ° C The bottle obtained as described above was repeatedly dropped. The test was performed according to the method described above. Table 2 shows the results.

The obtained bottle had no shark skin and had a good appearance.

[0088]

Example B3 70 parts by weight of HDPE (4) and M-LLD
Using a single screw extruder, 30 parts by weight of PE (4)
The mixture was melt-kneaded at a temperature of 0 ° C. to prepare a polyethylene composition. The resulting polyethylene composition had an intrinsic viscosity of 1.85 dl / g measured in a decalin solvent at 135 ° C. and a density (AS
TM D 1505) was 948 kg / m ³ .

Next, this polyethylene composition was blow-molded using an extrusion blow-molding machine under the same molding conditions as in Example B1, to obtain a bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 2 shows the results.

The obtained bottle had no shark skin and good appearance.

[0091]

Embodiment B4 In the embodiment B1, the HDPE (4) 9
Using 80 parts by weight of HDPE (6) instead of 0 parts by weight,
A polyethylene composition was prepared in the same manner as in Example B1, except that the amount of M-LLDPE (3) was changed to 20 parts by weight. The obtained polyethylene composition was 135 ° C.
1.90 dl / g intrinsic viscosity measured in decalin solvent
And the density (ASTM D 1505) was 939 kg / m ³ .

Next, the polyethylene composition was blow-molded using an extrusion blow molding machine under the following molding conditions.
A bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g was obtained. <Blow molding conditions> Molding temperature of polyethylene composition (resin): 200 ° C Resin pressure: 280 kg / m ² Resin extrusion rate: 50 kg / hr Mold temperature: 20 ° C The bottle obtained as described above was repeatedly dropped. The test was performed according to the method described above. Table 2 shows the results.

The obtained bottle had no shark skin and had a good appearance.

[0094]

Comparative Example B1 The procedure of Example B1 was repeated, except that the HDPE (5) was used in place of the polyethylene composition of Example B1, and the content was 780 m.
1, a bottle (single-layer hollow molded body) weighing 25 g was obtained. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 2 shows the results.

The obtained bottle had no shark skin and good appearance.

[0096]

Comparative Example B2 The procedure of Example B1 was repeated, except that the HDPE (6) was used in place of the polyethylene composition of Example B1, and the content was 780 m.
1, a bottle (single-layer hollow molded body) weighing 25 g was obtained. The obtained bottle was repeatedly subjected to a drop test according to the above method. Table 2 shows the results.

[0097] The obtained bottle had no shark skin and had a good appearance.

[0098]

Comparative Example B3 In Example B1, the amount of HDPE (4) was changed to 80 parts by weight, and M-LLDPE (3) 1
A polyethylene composition was obtained in the same manner as in Example B1, except that 20 parts by weight of T-LLDPE was used instead of 0 parts by weight. The resulting polyethylene composition had an intrinsic viscosity of 1.92 dl / g and a density (ASTM D 1505) of 948 kg / m ³ measured in a decalin solvent at 135 ° C.

Next, this polyethylene composition was blow-molded using an extrusion blow molding machine under the following molding conditions.
A bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g was obtained. <Blow Molding Conditions> Molding temperature of polyethylene composition (resin): 200 ° C. Resin pressure: 320 kg / m ² Resin extrusion amount: 50 kg / hr Mold temperature: 20 ° C. The bottle obtained as described above is repeatedly dropped. The test was performed according to the method described above. Table 2 shows the results.

The obtained bottle had no shark skin and had a good appearance.

[0101]

Comparative Example B4 In Example B1, the amount of HDPE (4) was changed to 70 parts by weight, and M-LLDPE (3) 1
A polyethylene composition was obtained in the same manner as in Example B1, except that 30 parts by weight of M-LLDPE (5) was used instead of 0 parts by weight. The resulting polyethylene composition was 135
The limiting viscosity measured in decalin solvent at 1.degree.
g and a density (ASTM D 1505) of 951 kg / m ³ .

Next, this polyethylene composition was blow-molded using an extrusion blow molding machine under the following molding conditions.
A bottle (single-layer hollow molded body) having an inner capacity of 780 ml and a weight of 25 g was obtained. <Blow Molding Conditions> Molding temperature of polyethylene composition (resin): 200 ° C. Resin pressure: 320 kg / m ² Resin extrusion amount: 50 kg / hr Mold temperature: 20 ° C. The bottle obtained as described above is repeatedly dropped. The test was performed according to the method described above. Table 2 shows the results.

The obtained bottle had no shark skin and had a good appearance.

[0104]

Comparative Example B5 In Example B1, HDPE (4) 9
Using 80 parts by weight of HDPE (6) instead of 0 parts by weight,
T-LLD instead of 10 parts by weight of M-LLDPE (3)
A polyethylene composition was obtained in the same manner as in Example B1, except that 20 parts by weight of PE (2) was used.

The obtained polyethylene composition was heated at 135 ° C.
1.90 dl / g intrinsic viscosity measured in decalin solvent
And the density (ASTM D 1505) was 939 kg / m ³ . Next, this polyethylene composition was blow-molded using an extrusion blow-molding machine under the following molding conditions.
A bottle (single-layer hollow molded body) weighing 80 ml and weighing 25 g was obtained. <Blow Molding Conditions> Molding temperature of polyethylene composition (resin): 200 ° C. Resin pressure: 320 kg / m ² Resin extrusion amount: 50 kg / hr Mold temperature: 20 ° C. The bottle obtained as described above is repeatedly dropped. The test was performed according to the method described above. Table 2 shows the results.

The obtained bottle had no shark skin and had a good appearance.

[0107]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08J 5/00 CES C08L 23/06 4J028 C08L 23/06 23/08 4J100 23/08 B29K 23:00 4J128 / / B29K 23:00 B29L 9:00 B29L 9:00 22:00 22:00 B65D 1/00 B (72) Inventor Yoshitaka Waga 3 Chigusa Kaigan, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Tetsuya Nakamura 3 Chigusa Coast, Ichihara-shi, Chiba F-term in Mitsui Chemicals Co., Ltd. (reference) GB16 JA06A JA07A JA15A JK10 YY00A 4F208 AA04C AA07 AG03 AG07 AH55 AR15 AR17 AR18 LB01 LB22 LG01 4J002 BB031 BB032 BB051 BB151 BB152 GF00 GG01 4J028 AA01A A A02A AB00A AB01A AC01A AC19A AC27A BA00A BA01B BA02B BA03B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC24B BC25B EA01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EC02 FA02 FA04 GA01 GA04 GA06 GA07 GA08 GA21 4J100 AA02P AA03Q AA04Q AA07Q AA08Q AA09Q AA15Q AA16Q AA17Q AA18Q AA19Q AA21Q CA01 CA04 DA04 DA09 DA13 DA14 DA15 DA40 DA52 DA64 FA10 JA58 4J128 AA01 AA02 AB00 AB01 AC01 AC19 AC27 AD00 BA00A BA01B BA02B BA03B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC24B BC25B EA01 GA04 EB02 FA04 EB02 FA04 GA08 GA21

Claims (20)

[Claims] (1) a density (ASTM D1505) of 920 to 940 kg;
/ M ³ , the intrinsic viscosity [η] (unit: dl / g) measured in a decalin solvent at 135 ° C. is in the range of 1.6 <[η] <10, and the melt flow rate (MFR; ASTM) D 1238, 190 ° C, 2.
16 kg load, unit: g / 10 min) and the intrinsic viscosity [η]
(Unit: dl / g) is ([MFR] / 10) ^{-(1 / 1.8)} >[η]> ([MFR]
/ 10) A resin for a polyethylene hollow molded body, which is a polyethylene satisfying the formula of ^{(1 / 4.8)} . 2. The method according to claim 1, wherein the polyethylene is ASTM D123.
8 (190 ° C.) and the melt flow rate (MFR _21.6 ) measured under a load of _21.6 kg was _2.16 k.
The value [(MFR _21.6 ) / (MFR _2.16 )] divided by the value of the melt flow rate (MFR _2.16 ) measured by the g load is
The resin for a polyethylene hollow molded article according to claim 1, wherein the resin is more than 30 polyethylene. 3. The polyethylene has a density (ASTM D 1505) of 940 kg / m ³ or more.
The intrinsic viscosity [η] measured in a decalin solvent at 35 ° C. is 1.
It is prepared using a high density polyethylene (A) of 5 to 5 dl / g and a metallocene olefin polymerization catalyst,
And the density (ASTM D 1505) is less than 920 kg / m ³ , and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C.
Is a linear low-density polyethylene (B) having a content of 1.0 to 10 dl / g, wherein the content of the linear low-density polyethylene (B) in the polyethylene composition is high. The amount is 2 to 30 parts by weight based on 100 parts by weight of the total of the high density polyethylene (A) and the linear low density polyethylene (B).
The resin for a polyethylene hollow molded article according to 1. 4. The G of said linear low density polyethylene (B)
Molecular weight distribution (Mw / Mn) measured by PC is 2
5. The resin for a polyethylene hollow molded article according to claim 3. 5. The polyethylene hollow according to claim 3, wherein the linear low-density polyethylene (B) has a normal temperature n-decane-soluble component fraction (W) of 0 to 15% by weight. Molded resin. 6. A single-layer bottle (content) wherein the polyethylene composition has a drop height of 1.8 m or more such that water filled in the bottle does not leak outside in a repeated drop test five times in an atmosphere of 0 ° C. The resin for a polyethylene hollow molded article according to claim 3, which is a polyethylene composition capable of being subjected to a hollow molding in an amount of 780 ml and a tare weight of 25 g). 7. A hollow polyethylene molded article comprising a layer comprising the resin for a polyethylene hollow molded article according to any one of claims 1 to 6. 8. The polyethylene hollow molded article according to claim 7, wherein the polyethylene hollow molded article is a container, and the average container weight per 100 cc of the tare is 4 g or less. 9. The polyethylene hollow molded article according to claim 7, wherein said hollow molded article is a multilayer container. 10. The polyethylene hollow molded article according to claim 7, wherein said hollow molded article is a container for a surfactant. 11. The polyethylene hollow molded article according to claim 7, wherein said hollow molded article is a bleach container. 12. A density (ASTM D 1505) of 940 kg / m ³
It is prepared using a high-density polyethylene (A) having an intrinsic viscosity [η] of 1.5 to 5 dl / g measured in a decalin solvent at 135 ° C. and a metallocene olefin polymerization catalyst,
And the density (ASTM D 1505) is less than 920 kg / m ³ , and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C.
Is a linear low-density polyethylene (B) having a content of 1.0 to 10 dl / g, wherein the content of the linear low-density polyethylene (B) in the polyethylene composition is high. A resin for a polyethylene hollow molded body, which is 2 to 30 parts by weight based on 100 parts by weight of the total of the high density polyethylene (A) and the linear low density polyethylene (B). 13. The linear low-density polyethylene (B) having a molecular weight distribution (Mw / Mn) measured by GPC of 2
13. The resin for a polyethylene hollow molded article according to claim 12, wherein 14. The polyethylene hollow according to claim 12, wherein the linear low-density polyethylene (B) has a normal temperature n-decane-soluble component fraction (W) of 0 to 15% by weight. Molded resin. 15. The intrinsic viscosity [η] of the mixture of the high-density polyethylene (A) and the linear low-density polyethylene (B) measured at 135 ° C. in a decalin solvent is 1.3 to 10 dl.
/ G and a density (ASTM D 1505) of 890-9.
13. The resin for a polyethylene hollow molded article according to claim 12, wherein the resin is 62 kg / m ³ . 16. A single-layer bottle (content) in which the polyethylene composition has a drop height of not less than 1.8 m such that water filled in the bottle does not leak outside in a repeated drop test five times in an atmosphere of 0 ° C. The resin for a polyethylene hollow molded article according to claim 12, which is a polyethylene composition capable of being subjected to a hollow molding in an amount of 780 ml and a tare weight of 25 g). 17. A polyethylene hollow molded article having a layer made of the resin for a polyethylene hollow molded article according to any one of claims 12 to 16. 18. The polyethylene hollow molded article according to claim 17, wherein said hollow molded article is a multilayer container. 19. The polyethylene hollow molded article according to claim 17, wherein the hollow molded article is a container for a surfactant. 20. The polyethylene hollow molded article according to claim 17, wherein the hollow molded article is a bleach container.