JP2014019806A - Polyethylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene-based resin composition in which balance between rigidity and a long period creep property is excellent, and surface appearance is favorable.SOLUTION: A polyethylene resin composition includes 10-90 wt.% of an ethylene homopolymer in which a solution viscosity [η]is 0.3-2.0 dl/g, and a density dis at least 950 kg/m; 90-10 wt.% of an ethylene/α-olefin copolymer produced by a specific metallocene catalyst in which a solution viscosity [η]is 1.0-6.0 dl/g, a density dis 910-955 kg/m, and satisfies a relation [η]>[η], d>d, wherein a density is 935-965 kg/m, a melt flow rate is 0.01-5 g/10 min, and tensile yield intensity (σ) and breaking time (t) in a whole circumference notch type tensile creep testing satisfy σ≥-3.1 log(t)+31.1, and the polyethylene resin composition is used.

Description

  The present invention relates to a polyethylene resin composition having excellent long-term creep properties. More specifically, the present invention relates to a polyethylene resin composition having an excellent balance between rigidity and long-term creep properties and excellent moldability.

  Polyethylene resin has excellent mechanical properties such as rigidity, impact resistance, environmental stress crack resistance (ESCR), and elongation characteristics, and also has excellent chemical resistance, corrosion resistance, and electrical properties. Widely used in fields such as film, sheet, pipe and blow container.

  However, recently, from the viewpoint of consideration of environmental issues and ease of handling, there is a high demand for thinner and lighter products. Sufficient strength can be obtained even when the thickness is reduced, and long-term creep properties such as ESCR are achieved. Also, an excellent polyethylene resin is desired. From the viewpoint of product productivity, there is a demand for a polyethylene resin that is excellent in molding processability, which can reduce the load during the molding process, increase the production speed, and cause less appearance defects.

  Generally, in order to maintain product strength by reducing the wall thickness, it is necessary to increase the rigidity (that is, the density of polyethylene), but long-term creep is incompatible with the density, and corresponds to thinning. Therefore, when the density of polyethylene is increased, there is a problem that long-term creep properties such as ESCR are insufficient. Further, in order to improve the moldability, it is basically necessary to lower the molecular weight, but in this case also the long-term creep property is lowered. Therefore, it has been difficult to obtain a polyethylene resin satisfying all of rigidity, molding processability, and long-term creep property by the conventional technique.

  In recent years, polyethylene resins have been developed in which a low molecular weight component and a high molecular weight component are produced separately and a comonomer is introduced only into the high molecular weight component to improve the balance of rigidity, moldability, and long-term creep properties ( For example, see Patent Document 1.) However, even in the case where such a device is applied, in applications where high rigidity is required, long-term creep properties such as ESCR are insufficient, and moldability is lowered by increasing the molecular weight in order to improve long-term creep properties. The problem still exists.

JP 2000-109521 A

  An object of the present invention is to provide a novel polyethylene resin composition that is superior in balance of rigidity, moldability, and long-term creep properties as compared with conventional polyethylene.

  As a result of intensive studies, the present inventors have found that in a polyethylene resin composition having a molecular weight distribution consisting of two components, an ethylene polymer A (low molecular weight component) and an ethylene polymer B (high molecular weight component), By polymerizing a high molecular weight component using a specific metallocene catalyst, it has been found that excellent long-term creep properties are expressed while maintaining good moldability even if the rigidity is higher than that of conventional resins. The present invention has been completed.

That is, the present invention relates to (1) an ethylene homopolymer (referred to as ethylene polymer A) 10 having a solution viscosity [η] _A of 0.3 to 2.0 dl / g and a density d _A of 950 kg / m ³ or more. and 90 wt%, the solution viscosity _{[eta] B} is 1.0~6.0dl / g, a density _{d B} is 910~955kg / ^{m 3,} weight average molecular weight determined by gel permeation chromatography (GPC) Copolymer of ethylene having a molecular weight distribution (Mw / Mn), which is the ratio of (Mw) and number average molecular weight (Mn), greater than 3 and an α-olefin having 3 to 20 carbon atoms (referred to as ethylene polymer B) 90% to 10% by weight (the total amount of the ethylene polymer A and the ethylene polymer B is 100% by weight). (2) The solution viscosity is [η] _B > [η] _A , and the density is d _A > satisfy a relationship of _{d B,} (3) density A 35~965kg / ^{m 3,} (4) melt flow rate (MFR) was 0.01~5g / 10min, (5) Tensile Tensile yield strength was determined by the test (sigma _y) and full notch formula In a tensile creep test, the fracture time (t _f ) measured in a 2% aqueous surfactant solution at a measurement temperature of 80 ° C. and a load stress of 5.4 MPa is σ _y ≧ −3.1 log (t _f ) +31.1
It is related with the polyethylene resin composition characterized by satisfying the following relationship.

  The present invention is described in detail below.

  First, the ethylene polymers A and B constituting the polyethylene resin composition of the present invention will be described.

(Ethylene polymer A)
The ethylene polymer A in the present invention is an ethylene homopolymer. The solution viscosity ([η] _A ) of the ethylene polymer A is 0.3 to 2.0 dl / g, preferably 0.35 to 1.0 dl / g, more preferably 0.4 to 0.8 dl / g. is there. Here, the solution viscosity is a value measured at 135 ° C. using orthodichlorobenzene (ODCB) as a solvent. [Η] When _A is less than 0.3 dl / g, mechanical strength such as impact resistance is lowered, and it is not preferable because smoke and scum are easily generated during molding. On the other hand, when [η] _A exceeds 2.0 dl / g, the fluidity at the time of molding processing decreases.

The density d A of the ethylene polymer _A is 950 kg / m ³ or more, preferably 960 kg / m ³ or more, more preferably 970 kg / m ³ or more. Here, the density is a value measured by the method shown in the examples. When the density is less than 950 kg / m ³ , the high-rigidity polyethylene resin targeted by the present invention cannot be obtained.

(Ethylene polymer B)
The ethylene polymer B in the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Here, examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like, and these may be used alone or in combination of two or more. Can be used. Of these α-olefins, 1-butene, 1-pentene, 1-hexene, and 1-octene are particularly preferable from the viewpoint of excellent balance between rigidity and long-term creep property.

  In addition, it is preferable that the C3-C20 alpha-olefin content contained in the ethylene-type polymer B is 8 wt% or less from the point which obtains the highly rigid polyethylene resin made into the objective of this invention.

The solution viscosity ([η] _B ) of the ethylene polymer B is 1.0 to 6.0 dl / g, preferably 2.0 to 5.5 dl / g, more preferably 3.0 to 5.0 dl / g. is there. [Η] When _B is less than 1.0 dl / g, excellent long-term creep properties cannot be obtained. On the other hand, when [η] _B exceeds 6.0 dl / g, the fluidity during the molding process is lowered and an unmelted gel is likely to be generated.

The density dB of the ethylene polymer _B is 910 to 955 kg / m ³ , preferably 912 to 945 kg / m ³ , more preferably 915 to 935 kg / m ³ . When the density is less than 910 kg / m ³ , the highly rigid polyethylene resin targeted by the present invention cannot be obtained. On the other hand, when the density exceeds 955 kg / m ³ , the long-term creep property becomes insufficient.

  Mw / Mn of the ethylene polymer B is greater than 3, preferably greater than 3.5, and more preferably greater than 4. When Mw / Mn of the ethylene polymer B is 3 or less, the moldability of the polyethylene resin composition is reduced.

  Next, the polyethylene resin composition of the present invention will be described. The polyethylene resin composition of the present invention is composed of the aforementioned ethylene polymer A and ethylene polymer B. The composition ratio of the ethylene polymer A and the ethylene polymer B is such that the ethylene polymer A is 10 to 90% by weight and the ethylene polymer B is 90 to 10% by weight, preferably the ethylene polymer A is The ethylene polymer B is 80 to 20% by weight with respect to 20 to 80% by weight, and more preferably the ethylene polymer A is 30 to 70% by weight with respect to 30 to 70% by weight (ethylene The total amount of the polymer A and the ethylene polymer B is 100% by weight). When the ethylene-based polymer B exceeds 90% by weight (that is, when the ethylene-based polymer A is less than 10% by weight), the fluidity during the molding process is lowered. On the other hand, when the ethylene polymer B is less than 10% by weight (that is, when the ethylene polymer A exceeds 90% by weight), the mechanical strength of the polyethylene resin is lowered, and the object of the present invention is excellent. Long-term creep cannot be obtained.

The solution viscosity ([η] _A ) of the ethylene polymer _A and the solution viscosity ([η] _B ) of the ethylene polymer B must satisfy the relationship [η] _B > [η] _A. When this relationship is not satisfied, a polyethylene resin composition excellent in the balance between rigidity and long-term creep property, which is the object of the present invention, cannot be obtained.

The density (d _A ) of the ethylene polymer _A and the density (d _B ) of the ethylene polymer B must satisfy the relationship d _A > d _B. When this relationship is not satisfied, a polyethylene resin composition excellent in the balance between rigidity and long-term creep property, which is the object of the present invention, cannot be obtained.

The density of the polyethylene resin composition of the present invention is 935 to 965 kg / m ^3, preferably 940 to 960 kg / m ³ , more preferably 945 to 958 kg / m ³ . When the density is less than 935 kg / m ³ , the high-rigidity polyethylene resin targeted by the present invention cannot be obtained. On the other hand, when the density exceeds 965 kg / m ³ , the long-term creep property becomes insufficient.

  The MFR of the polyethylene resin composition of the present invention is 0.01 to 5 g / 10 min, preferably 0.02 to 2 g / 10 min, more preferably 0.05 to 1 g / 10 min. Here, MFR is a value when measured under conditions of a load of 2.16 kg and a temperature of 190 ° C. When the MFR is less than 0.01 g / 10 min, the fluidity is poor and processing with a normal molding machine is extremely difficult. On the other hand, when the MFR exceeds 5 g / 10 min, the mechanical strength is lowered, and the excellent long-term creep property of the present invention cannot be obtained.

The polyethylene resin composition of the present invention has a tensile yield strength (σ _y ) measured by a tensile test and a circumferential notch tensile creep test in a 2% surfactant aqueous solution, a measurement temperature of 80 ° C., and a load stress of 5.4 MPa. The fracture time (t _f ) measured in (1) is σ _y ≧ −3.1 log (t _f ) +31.1 (1)
Preferably σ _y ≧ −3.1 log (t _f ) +32.7 (1)
More preferably, σ _y ≧ −3.1 log (t _f ) +34.3 (1 ”)
It is necessary to satisfy the relationship.

Here, the tensile yield strength (σ _y ) was measured at a test temperature of 23 using a test piece punched into a dumbbell shape after press-molding the polyethylene resin composition of the present invention into a sheet shape by the method shown in the Examples. It can be determined by conducting a tensile test at a temperature of 200 ° C. and a strain rate of 200% / min.
The fracture time (t _f ) was determined by the method shown in the examples by using the test piece punched into the above-mentioned dumbbell shape and referring to the method described in Annex 5 of JIS K6774. It can be obtained by conducting a test.

Equation (1) is obtained experimentally. The slope (-3.1) of the formula (1) was calculated from the approximate straight line by regression analysis of the relationship between the tensile yield strength (σ _y ) and the fracture time (t _f ) of Examples 1 to 4. Further, in the intercept (31.1) of the formula (1), the relationship between the tensile yield strength (σ _y ) and the fracture time (t _f ) of all the polyethylene resin compositions of the present invention satisfies the formula (1). Thus, it determined by moving the approximate straight line obtained by the regression analysis of Examples 1-4.

The tensile yield strength (σ _y ) correlates with the density and becomes an index of the rigidity of the molded body obtained from the polyethylene resin composition of the present invention. Further, it is known that the all-around notch type tensile creep test has a strong correlation with the hot internal pressure creep test widely adopted as an effective method for evaluating the long-term creep property of the pipe (JIS K 6774 (1998). ) Polyethylene pipe for gas Japanese Standards Association (see 1998), and the obtained fracture time (t _f ) is an indicator of long-term creep properties. Therefore, it can be said that the polyethylene resin composition of the present invention satisfying the above-described formula (1) is excellent in the balance between rigidity and long-term creep property.

Even when the tensile yield strength (σ _y ) is the same, the breaking time (t _f ) is affected by the MFR of the polyethylene resin composition, and the lower the MFR, the longer the breaking time (t _f ). Therefore, if the MFR is lowered, it is possible to satisfy the above-described formula (1), but in that case, the molding processability is lowered, and the processing by a normal molding machine becomes extremely difficult. The polyethylene resin composition of the present invention is required to satisfy the above-mentioned formula (1) when the MFR having no problem in molding processability is 0.01 g / 10 min or more, whereby rigidity, molding processability, long-term creep are required. A polyethylene resin composition balanced at a high level is obtained.

  Next, a catalyst and a production method for obtaining the polyethylene resin composition of the present invention will be described.

  The ethylene-based polymer A in the present invention can be an ethylene-based polymer produced by a slurry polymerization method using a Ziegler-Natta catalyst. However, a metallocene catalyst other than a Ziegler-Natta catalyst, a Philips chrome-based polymer. It is also possible to use an ethylene polymer obtained by a catalyst.

  The production of the ethylene-based polymer A according to the present invention can be carried out under the general reaction conditions of a slurry method using a so-called Ziegler-Natta catalyst. That is, polymerization is carried out at a temperature of 20 to 110 ° C. in a continuous or batch manner. The polymerization pressure is not particularly limited, but it is particularly suitable to use 0.15 to 5 MPa under pressure. As the solvent for carrying out the polymerization, any commonly used solvent can be used. Particularly suitable are alkanes or cycloalkanes having 3 to 20 carbon atoms, such as propane, isobutane, pentane, hexane, cyclohexane and the like.

  The production of the ethylene-based polymer A includes not only ethylene homopolymerization but also copolymerization of ethylene and one or more α-olefins. Examples of the α-olefin used for the polymerization include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like. These may be used alone or in combination of two or more. Can be used. Moreover, in order to introduce a double bond into the polymer, copolymerization can also be performed using a mixture of an α-olefin and a diene such as butadiene or isoprene. The amount of α-olefin used for copolymerization needs to be selected according to the density of the target polymer.

  The production of the ethylene-based polymer A can be performed not only in one-stage polymerization performed under one normal polymerization condition but also in multi-stage polymerization performed under a plurality of polymerization conditions.

  The molecular weight of the ethylene-based polymer A can be adjusted by a known means, that is, a method in which an appropriate amount of hydrogen is present in the reaction system.

  The density can be adjusted by the α-olefin concentration in the reaction system during the production of the ethylene polymer A described later. That is, the density can be reduced by increasing the α-olefin to be added and increasing the α-olefin concentration. It is also possible to increase the density by reducing the added α-olefin.

[Η] _A can be adjusted by the hydrogen concentration in the reaction system when the ethylene polymer A is produced. [Η] _A can be reduced by increasing the amount of hydrogen to be added and increasing the hydrogen concentration. It is also possible to increase [η] _A by reducing the amount of hydrogen to be added. [Η] _A can also be adjusted by the polymerization reaction temperature during the production of the ethylene-based polymer A, and [η] _A can be increased by setting the temperature to a lower temperature. The ethylene-based polymer B in the present invention comprises ethylene produced by a metallocene catalyst containing a component (a) a metallocene compound, a component (b) an organically modified clay, and a component (c) an organoaluminum compound, and α having 3 to 20 carbon atoms. -Copolymers with olefins. The ethylene polymer obtained by a general metallocene catalyst represented by a catalyst comprising a metallocene compound, an aluminoxane and an inorganic oxide carrier has a weight average molecular weight (Mw) and number measured by gel permeation chromatography (GPC). An ethylene system produced with a metallocene catalyst comprising component (a), component (b) and component (c), whereas the molecular weight distribution, which is the ratio (Mw / Mn) of the average molecular weight (Mn), is 3 or less The Mw / Mn of the polymer B becomes larger than 3, which improves the moldability of the polyethylene resin composition containing the ethylene polymer B.

  The component (a) in the present invention is a metallocene compound, specifically, the general formula (6) or (7)

で表されるメタロセン化合物を例示することができ、好ましくは、剛性、成形加工性、長期クリープ性のバランスに優れたポリエチレン樹脂組成物を得ることを目的に、一般式（７）で表されるメタロセン化合物を用いることが好ましい。

The metallocene compound represented by general formula (7) is preferable, and is preferably represented by the general formula (7) for the purpose of obtaining a polyethylene resin composition having an excellent balance of rigidity, moldability, and long-term creep property. It is preferable to use a metallocene compound.

M ¹ is a titanium atom, a zirconium atom, or a hafnium atom, and each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atom. 20 alkylamino groups and C1-C20 alkylsilyl groups.

R ¹ and R ² in the formula (6) are each independently a ligand coordinated to M ¹ represented by the following general formula (8), (9), (10) or (11),

Ｒ^１とＲ^２はＭ^１と一緒にサンドイッチ構造を形成し、Ｒ^６は各々独立して、水素原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基である。

R ¹ and R ² form a sandwich structure with M ^1, and R ⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. An alkylamino group having -20 carbon atoms and an alkylsilyl group having 1-20 carbon atoms.

R ³ and R ⁴ in the formula (7) are each independently a ligand coordinated to M ¹ represented by the following general formula (12), (13), (14) or (15),

Ｒ^３とＲ^４はＭ^１と一緒にサンドイッチ構造を形成し、Ｒ^７は各々独立して、水素原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基である。

R ³ and R ⁴ form a sandwich structure with M ^1, and R ⁷ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. An alkylamino group having -20 carbon atoms and an alkylsilyl group having 1-20 carbon atoms.

R ⁵ in the formula (7) is represented by the general formula (16) or (17)

で表され、Ｒ^３とＲ^４を架橋するように作用しており、ｎは１〜５の整数であり、Ｒ^８は各々独立して、水素原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基であり、Ｍ^２はケイ素原子、ゲルマニウム原子または錫原子である。

In which R ³ and R ⁴ are cross-linked, n is an integer of 1 to 5, and R ⁸ is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms, and M ² is a silicon atom, a germanium atom, or a tin atom.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms in the present invention include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2 , 2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, cyclohexyl group, vinyl Group, propenyl group, phenyl group, methylphenyl group and naphthyl group.

  As a C1-C20 alkoxy group in this invention, a methoxy group and an ethoxy group can be illustrated.

  Examples of the alkylamino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, and a di-n-propylamino group.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a phenyldimethylsilyl group, and a diphenylmethylsilyl group.

  As the compound represented by the general formula (6), bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopenta) Zirconium compounds such as dienyl) zirconium dichloride and bis (indenyl) zirconium dichloride, compounds in which the zirconium atom is changed to titanium atom, hafnium atom, and the dichloro form of the above metallocene compounds are dimethyl, diethyl, dihydro, diphenyl, dibenzyl The compound etc. which were changed into the body can be illustrated.

Compounds represented by the general formula (7) include methylene bis (methylcyclopentadienyl) zirconium dichloride, methylene bis (butylcyclopentadienyl) zirconium dichloride, methylene bis (tetramethylcyclopentadienyl) zirconium dichloride, ethylene bis (tetrahydro Indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl (2,7-dimethyl-) 9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride , Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (9-fluorene) ) Zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-) Fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zyl Conium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (2 , 7-di-t-butyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) ) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene ( 2-Methyl-4,5-benzo 1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (2-methyl) -4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopenta) Dienyl) zirconium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethyl Randiylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) Zirconium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (1-indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride, dimethylsilanediylbis (Tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, di Methylsilanediyl (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, Dimethylsilanediyl (cyclopentadienyl) (1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4 7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) ) (7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-phenyl-1- Indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methyl1-indenyl) zirconium Dichloride, dimethylsilanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methyl 1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (7-methyl-1-in Nyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride Dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethyl-1-indenyl) zirconium dichloride, dimethyl Silanediyl (cyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxy-7-methyl-1-indenyl) Zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7-trimethyl) -1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7) -Methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethyl) Clopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethylsilane Diylbis (butylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, Diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) Luconium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (1-indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl Bis (tetrahydro-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethyl Silanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl) (1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4,7-dimethyl -1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) ) Zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-phenyl-1-indenyl) zirconi Mudichloride, diethylsilanediyl (cyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methyl1-indenyl) zirconium dichloride, diethyl Silanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methyl1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl ( Tetramethylcyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride Diethylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethyl-1-indenyl) zirconium dichloride, Diethylsilanediyl (cyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4-methoxy-7-methyl-1-indenyl) zirconium dichloride, Diethylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7-trimethyl-1- Inde Nyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7-methyl-) 1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (2,4,4) 7-trimethylindenyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride , Diphenylsilanediylbis (butylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) Zirconium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopenta) Dienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-1-yne) Nyl) zirconium dichloride, diphenylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9fluorenyl) ) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (1-indenyl) zirconium dichloride, diphenylsilanediyl (Cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4,7 -Dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7-methyl-1 -Indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7-phenyl-1-indenyl) zirconium dichloride, diphenylsilane Diyl (cyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methoxy-7-methyl 1-indenyl) di Conium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methyl1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride Diphenylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (Cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethyl-1-yne) Nyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-methoxy-7-methyl-1- Indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7 -Trimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclone) Lopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetra Zirconium compounds such as methylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, compounds in which zirconium atoms are changed to titanium atoms and hafnium atoms, and dichloro bodies of the above transition metal compounds are dimethyl bodies and diethyl bodies. , Dihydro isomer, diphenyl isomer, compound changed to dibenzyl isomer, etc., preferably, for the purpose of obtaining a polyethylene resin composition excellent in the balance of rigidity, moldability, and long-term creep property, Diphenylme Len (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride can be used.

  Component (b) in the present invention is an organic modified clay obtained by modifying a clay compound with an organic compound, and is an ionic complex in which organic ions are introduced between clay compound layers.

  Clay compounds used for modification of clay compounds are fine particles mainly composed of microcrystalline silicate, and have a layered structure as a structural feature, and many of them have various sizes in the layer. Have a negative charge. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica, alumina or zeolite. When the clay compounds are classified according to the magnitude of the negative charge described above, the pyrophyllite, kaolinite, dickite and talc groups in which the negative charge per chemical formula is 0, and the smectite group in which the negative charge is 0.25 to 0.6 , 0.6 to 0.9 vermiculite group, approximately 1 mica group, approximately 2 brittle mica group. Each group shown here includes various minerals, and examples of clay minerals belonging to smectite include montmorillonite, beidellite, saponite, hectorite and the like. Moreover, although these clay compounds exist naturally, those with few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay compounds shown here and the clay compounds obtained by artificial synthesis can be used, and those not included in the above examples are also used. it can. In order to increase the molecular weight distribution of the ethylene polymer B for the purpose of obtaining a polyethylene resin composition excellent in molding processability, a clay compound belonging to a smectite group hectorite is suitable.

  As the organic compound used for the modification of the clay compound, a compound represented by the following general formula (18) is suitable for the purpose of obtaining a polyethylene resin composition having an excellent balance of rigidity, moldability, and long-term creep property. is there.

式（１８）中のＲ^９〜Ｒ^１１は各々独立して炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数１〜３０のアルキルアミノ基、炭素数１〜３０のアルキルシリル基であり、剛性、長期クリープ性のバランスに優れたポリエチレン樹脂組成物を得ることを目的に、少なくともひとつが炭素数１４以上であれば好適であり、少なくともひとつが炭素数２１以上であればさらに好適である。また、成形加工性に優れたポリエチレン樹脂組成物を得ることを目的に、エチレン系重合体ＢのＭｗ／Ｍｎを大きくするためにＲ^９〜Ｒ^１１の炭素数を低減することもできる。

R ^{9 to} R ¹¹ in formula (18) are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and 1 to 30 carbon atoms. For the purpose of obtaining a polyethylene resin composition having an excellent balance of rigidity and long-term creep properties, it is preferable that at least one has 14 or more carbon atoms, and at least one has 21 or more carbon atoms. It is more preferable if it exists. In order to increase the Mw / Mn of the ethylene-based polymer B for the purpose of obtaining a polyethylene resin composition excellent in molding processability, the carbon number of R ^{9 to} R ¹¹ can be reduced.

M ³ in the formula (18) is an atom belonging to Group 15 of the periodic table, and R ⁹ R ¹⁰ R ¹¹ HM ³⁺ is a monovalent cation.

A ⁻ is a monovalent anion, such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetra A fluoroborate ion or a hexafluorophosphate ion can be exemplified, but is not limited thereto.

Examples of the hydrocarbon group having 1 to 30 carbon atoms in the present invention include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4 -Methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, 2-methylcyclohexyl group 3-methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert-octyl group, 2,3-dimethylcyclohexyl Group, 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, n-tridecyl group, n- Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, oleyl group , Behenyl group, phenyl group and the like.
Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, and a phenoxy group.
Examples of the alkylamino group having 1 to 30 carbon atoms include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diisopropylamino group, a diphenylamino group, and a methylphenylamino group.

  The alkylsilyl group having 1 to 30 carbon atoms includes a trimethylsilyl group, a tritert-butylsilyl group, a ditert-butylmethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group. Can be illustrated.

Specific examples of the organic compound represented by the general formula (18) when M ³ is a nitrogen atom include N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N-methyl-Nn-propyl-behenylamine hydrochloride, N-methyl-N-isopropyl-behenylamine hydrochloride, N-methyl-Nn-butyl-behenylamine hydrochloride, N-methyl-Nn -Propyl-behenylamine hydrochloride, N-methyl-N-isobutyl-behenylamine hydrochloride, N-methyl-N-tert-butyl-behenylamine hydrochloride, N-methyl-Nn-pentyl-behenylamine hydrochloride N-methyl-N-isopentyl-behenylamine hydrochloride, N-methyl-N- (2-methylbutyl) -behenylamine hydrochloride, N-methyl-N-neopenty Ru-behenylamine hydrochloride, N-methyl-N-tert-pentyl-behenylamine hydrochloride, N-methyl-Nn-hexyl-behenylamine hydrochloride, N-methyl-N-isohexyl-behenylamine hydrochloride, N-methyl-Nn-heptyl-behenylamine hydrochloride, N-methyl-Nn-octyl-behenylamine hydrochloride, N-methyl-Nn-nonyl-behenylamine hydrochloride, N-methyl-N -N-decyl-behenylamine hydrochloride, N-methyl-Nn-undecyl-behenylamine hydrochloride, N-methyl-Nn-dodecyl-behenylamine hydrochloride, N-methyl-Nn-tetradecyl- Behenylamine hydrochloride, N-methyl-Nn-hexadecyl-behenylamine hydrochloride, N-methyl-Nn-octadecyl-behenylamine hydrochloride, -Methyl-Nn-nonadecyl-behenylamine hydrochloride, N-methyl-Nn-aralkyl-behenylamine hydrochloride, N-methyl-N-oleyl-behenylamine hydrochloride, N-methyl-N-allyl- Behenylamine hydrochloride, N-methyl-N-cyclopentyl-behenylamine hydrochloride, N-methyl-N-cyclohexyl-behenylamine hydrochloride N-methyl-N-3-methylcyclohexyl-behenylamine hydrochloride, N-methyl- N-4-methylcyclohexyl-behenylamine hydrochloride, N-methyl-N-2,3-dimethylcyclohexyl-behenylamine hydrochloride, N-methyl-N-cyclododecyl-behenylamine hydrochloride, N-methyl-N- Cyclododecyl-behenylamine hydrochloride, N-methyl-N-cyclododecyl-behenylamine hydrochloride, -Methyl-N-cyclododecyl-behenylamine hydrochloride N, N-diethyl-behenylamine hydrochloride, N-ethyl-N-ethyl-behenylamine hydrochloride, N-ethyl-Nn-propyl-behenylamine hydrochloride N-ethyl-N-isopropyl-behenylamine hydrochloride, N-ethyl-Nn-butyl-behenylamine hydrochloride, N-ethyl-Nn-propyl-behenylamine hydrochloride, N-ethyl-N- Isobutyl-behenylamine hydrochloride, N-ethyl-N-tert-butyl-behenylamine hydrochloride, N-ethyl-Nn-pentyl-behenylamine hydrochloride, N-ethyl-N-isopentyl-behenylamine hydrochloride, N-ethyl-N- (2-methylbutyl) -behenylamine hydrochloride, N-ethyl-N-neopentyl-behenylamine hydrochloride, N -Ethyl-N-tert-pentyl-behenylamine hydrochloride, N-ethyl-Nn-hexyl-behenylamine hydrochloride, N-ethyl-N-isohexyl-behenylamine hydrochloride, N-ethyl-Nn- Heptyl-behenylamine hydrochloride, N-ethyl-Nn-octyl-behenylamine hydrochloride, N-ethyl-Nn-nonyl-behenylamine hydrochloride, N-ethyl-Nn-decyl-behenylamine hydrochloride Salt, N-ethyl-Nn-undecyl-behenylamine hydrochloride, N-ethyl-Nn-dodecyl-behenylamine hydrochloride, N-ethyl-Nn-tetradecyl-behenylamine hydrochloride, N-ethyl -Nn-hexadecyl-behenylamine hydrochloride, N-ethyl-Nn-octadecyl-behenylamine hydrochloride, N-ethyl-Nn-nonadeci -Behenylamine hydrochloride, N-ethyl-Nn-aralkyl-behenylamine hydrochloride, N-ethyl-N-oleyl-behenylamine hydrochloride, N-ethyl-N-allyl-behenylamine hydrochloride, N-ethyl -N-cyclopentyl-behenylamine hydrochloride, N-ethyl-N-cyclohexyl-behenylamine hydrochloride, N-ethyl-N-3-methylcyclohexyl-behenylamine hydrochloride, N-ethyl-N-4-methylcyclohexyl- Behenylamine hydrochloride, N-ethyl-N-2,3-dimethylcyclohexyl-behenylamine hydrochloride, N-ethyl-N-cyclododecyl-behenylamine hydrochloride, N-ethyl-N-cyclododecyl-behenylamine hydrochloride N-ethyl-N-cyclododecyl-behenylamine hydrochloride, N-ethyl-N-cyclodode Ru-behenylamine hydrochloride, N-ethyl-N-cyclododecyl-behenylamine hydrochloride, N, N-dipropyl-behenylamine hydrochloride, N, N-dibutyl-behenylamine hydrochloride, N, N-dipentyl-behenyl Amine hydrochloride, N, N-dihexyl-behenylamine hydrochloride, N, N-diheptyl-behenylamine hydrochloride, N, N-dioctyl-behenylamine hydrochloride, N, N-dimethyl-hexatocosylamine hydrochloride, etc. Although the compound and the compound which replaced the hydrochloride of the said compound with the hydrofluoric acid salt, the hydrobromide, the hydroiodide, or the sulfate can be illustrated, it is not limited to these.

Examples of those in which M ³ is a phosphorus atom include compounds such as P, P-dimethyl-behenylphosphine hydrochloride, P, P-diethyl-behenylphosphine hydrochloride, P, P-dipropyl-behenylphosphine hydrochloride, Examples thereof include, but are not limited to, compounds in which hydrochloride is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

  In organic compound modification | denaturation, it is preferable to process by selecting the conditions of 0.1-30 weight% of clay compounds, and process temperature 0-150 degreeC. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay compound and the organic compound, in order to improve the activity of the catalyst, it is preferable to use an organic compound equivalent to or more than the exchangeable cation of the clay compound. In order to increase / Mn, the amount of the organic compound can be reduced. As the treatment solvent, aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or n-butyl ether, Halogenated hydrocarbons such as methylene chloride or chloroform, acetone, 1,4-dioxane, tetrahydrofuran, water or the like can be used, but preferably alcohols or water is used alone or as a component of a solvent. .

  Further, the particle size of the organically modified clay (b) used in the present invention is not particularly limited, but if it is too small, it will be difficult to settle and it will not be possible to efficiently prepare the catalyst. If it is too large, the catalyst will be transferred in a slurry. In order to clog the piping in the middle, it is preferably 1 to 100 μm. The method for adjusting the particle size is not particularly limited, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Also good. The particle size may be adjusted for unmodified clay or for modified organically modified clay.

  The method of pulverization and granulation is not particularly limited. For pulverization, impact mill, rotary mill, cascade mill, cutter mill, cage mill, impact pulverizer, conical mill, colloid mill, compound mill, jet mill, vibration mill, stamp mill , Tube mill, disk mill, tower mill, medium stirring mill, hammer mill, pin mill, fret mill, pebble mill, ball mill, ball mill, planetary mill, ring ball mill, ring roll mill, rod mill, roller mill, roll crusher etc. as granulation May be any method such as rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, melt granulation, spray granulation and the like.

  Component (c) in the present invention is a compound represented by the following general formula (19).

式中のＲ^１２は炭素数１〜２０の炭化水素基であり、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムを例示できる。

R ¹² in the formula is a hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum.

  Although there is no restriction | limiting in the ratio of the component (a) in this invention, a component (b), and a component (c), The ratio shown next is desirable. The molar ratio of component (a) to component (c) is in the range of (component (a)) :( component (c)) = 100: 1 to 1: 100000, in particular in the range of 1: 1 to 1: 10000. Preferably, the weight ratio of component (a) to component (b) is (component (a)) :( component (b)) = 10: 1 to 1: 10000, in particular 3: 1 to 1: 1000. It is preferable that it is the range of these.

  There is no restriction on the method for preparing the metallocene catalyst containing the component (a), component (b) and component (c) of the present invention. And a method of mixing them. Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare a metallocene catalyst using two or more kinds of component (b) and component (c).

  The method for producing the ethylene-based polymer B in the present invention can be used for any ordinary polymerization process, that is, any process of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization.

  The method for producing the ethylene-based polymer B in the present invention can be carried out either in the gas phase or in the liquid phase. In particular, when the polymerization is performed in the gas phase, the ethylene polymer having a uniform particle shape can be efficiently and stably produced. Can be produced. Further, when the polymerization is performed in a liquid phase, the solvent used may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Olefins such as 1-butene, 1-octene and 1-hexene can also be used as a solvent.

  In the method for producing the ethylene-based polymer B of the present invention, the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration are not particularly limited, but the polymerization temperature is −100 to 300 ° C., and the polymerization time is 10 seconds to For 20 hours, the polymerization pressure is preferably in the range of normal pressure to 3000 kg / cm 2 G. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The ethylene polymer obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

[Η] _B , like [η] _A , can be adjusted by the hydrogen concentration in the reaction system during the production of the ethylene polymer B and the polymerization reaction temperature. [Η] _B can also be controlled by the type of metallocene used in the production of the ethylene polymer B, and the metallocene compound of the general formula (7) is used rather than the metallocene compound of the general formula (6) described later. A higher [η] _B is obtained when used. In addition, [η] _B is higher when the metallocene compound having the ligand of the general formula (15) is used than the metallocene compound having the ligand of the general formulas (12), (13) and (14). It is done. Furthermore, [η] _B can be adjusted depending on the type of the organically modified clay (component (b)) used in the production of the ethylene polymer B, and is a compound represented by the general formula (18) described later used for modification. High [η] _B can also be obtained by reducing the amount added or by reducing the number of carbon atoms of the hydrocarbon groups (R ^{9 to} R ¹¹ ) in the general formula (18).

  The density can be adjusted by the α-olefin concentration in the reaction system when the ethylene polymer B is produced. That is, the density can be reduced by increasing the α-olefin to be added and increasing the α-olefin concentration. It is also possible to increase the density by reducing the added α-olefin. Furthermore, the density can be adjusted by the type of metallocene used in the production of the ethylene polymer B, and the one using the metallocene compound of the general formula (7) rather than using the metallocene compound of the general formula (6) described later. Gives a low density at the same α-olefin concentration. Further, when n is reduced in the metallocene compound of the general formula (7), the density of the ethylene polymer is reduced at the same α-olefin concentration, and the lowest density is obtained when n = 1.

  In the polyethylene resin composition of the present invention, the ethylene polymer A and the ethylene polymer B are polymerized using a single polymerizer, and the resulting mixture of the ethylene polymers A and B is uniaxial or multiaxial. Can be obtained by a melt kneading method using an extruder, or a melt kneading method using a known kneading apparatus such as a Banbury mixer, a kneader, or a roll. The polyethylene resin of the present invention can also be obtained by continuously polymerizing ethylene polymer A and ethylene polymer B by a multistage slurry polymerization method in which a plurality of polymerization vessels are connected in series. it can. In this case, there is no particular limitation on the polymerization order of the ethylene polymer A and the ethylene polymer B.

  The polyethylene resin composition of the present invention is an ethylene polymer obtained by a catalyst other than the catalyst used in the present invention and the production method, for example, a Ziegler other than the catalyst used in the present invention, as long as the effects of the present invention are not significantly impaired. -It can also be used by blending with an ethylene polymer obtained by a Natta catalyst, a metallocene catalyst, a Philips chrome catalyst, an ethylene polymer obtained by a high pressure radical method, or the like.

  Furthermore, the polyethylene resin composition of the present invention may contain various additives as necessary, for example, antioxidants, neutralizers, lubricants, weathering agents, antistatic agents, flame retardants, nucleating agents, crosslinking agents (peroxides). Etc.), carbon black, various pigments and various inorganic fillers such as talc, calcium carbonate, clay, mica, barium sulfate and magnesium hydroxide, conductive fillers such as metal fibers, and the like.

  The polyethylene resin composition obtained by the present invention is a known method conventionally used for molding a polyethylene resin, such as extrusion molding, blow molding, injection blow molding, injection molding, inflation molding, rotational molding, vacuum molding, etc. It can shape | mold by the method of.

  Since the polyethylene resin composition of the present invention has excellent long-term creep properties, it is possible to highly improve the balance of rigidity, molding processability and long-term creep properties as compared with conventional polyethylene, and pipes, sheets, Extrusion materials such as tapes, coating materials, industrial materials, detergent containers, chemical containers, medical containers, food containers, hollow molding materials such as various industrial materials, home appliance parts, industrial parts, containers, miscellaneous goods, etc. It is suitable as a material for a wide range of uses such as molding materials, various film materials, and various fiber materials. Further, it is excellent in the balance between rigidity and long-term creep property and has a good surface appearance, and is suitable as a material for polyethylene pipes suitable for gas transport pipes and water supply / drainage pipes.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

  Various measurement methods in Examples and Comparative Examples are shown below.

(1) Solution viscosity The solution viscosity was measured under the following conditions.
Apparatus: Capillary viscosity automatic measuring device SS 201-H2T manufactured by Shibayama Scientific Instruments Mfg. Co., Ltd.
Viscosity tube: Ubbelohde improved solvent: o-dichlorobenzene (with BHT 0.1%)
Measurement temperature: 135 ± 0.2 ° C
Calculation method: Mead & Fuoss formula (one-point method), average value of n = 2 (2) Density Predetermined annealing was performed on the extrudate of the MI meter, and measurement was performed with a density gradient tube.
(Conforms to JIS K6922-1, K6922-2, K7112)
(3) MFR
Measured with an MI meter at a measurement temperature of 190 ° C. and a load of 2.16 kg (conforming to JIS K6922-2, K7210)
(4) full notch type tensile failure time due to creep test _(t f)
[Measurement sample]
A dumbbell-shaped test piece with a parallel part length of 25 mm and a width of 5 mm is punched out from a 3.2 mm thick flat plate press-molded under the following conditions, and a 0.5 mm deep leather notch is placed in the center of the test piece on the entire circumference. Used.

Press temperature: 180 ° C
Cooling press temperature: 25 ° C / min
Preheating time: 5 min
Pressurization time: 5 min
Heating pressure: 200 kg / cm ² (gauge pressure)
[All-around notch tensile creep test]
The test piece is set in an all-around notch type tensile creep tester (Model TCT-6NC, manufactured by Daiichi Kagaku Co., Ltd.), measuring temperature 80 ° C., surfactant (Nonion NS-215, manufactured by NOF Corporation) In a 2% aqueous solution, n = 3 fracture time was measured by changing the load so that the load stress (the load / effective cross-sectional area excluding the notch portion) was in the range of 5.0 to 6.4 MPa. Calculated breaking time in the load stress 5.4MPa a (t _f) by the least square method from the relationship between the applied stress fracture time.

(5) Tensile yield strength (σ _y )
[Measurement sample]
A dumbbell-shaped test piece similar to that used in the all-around notch tensile creep test was used.

[Tensile test]
A test piece is set on a tensile tester (trade name Tensilon UTM-2.5T manufactured by Toyo Seiki Co., Ltd.), and the test is performed at a measurement temperature of 23 ° C. and a strain rate of 200% / min (tensile rate of 50 mm / min). The tensile yield strength (σ _y ) was calculated according to JIS K7113.

(6) Molding appearance A capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is equipped with a die having a length of 8 mm, a diameter of 2.095 mm, and an inflow angle of 90 °, and a measurement temperature of 190 ° C. The molten resin was extruded at a piston lowering speed of 100 mm / min (shear measurement: 152 sec ⁻¹ ), and the surface state of the obtained strand (string-shaped molded body) was visually observed. The case where the surface of the strand was smooth was marked with ◯, and the case where surface roughness occurred was marked with ×.

  Hereinafter, the methods for preparing the catalysts used in Examples and Comparative Examples will be described, but the present invention is not limited to these Examples.

Catalyst Preparation Example 1: Metallocene catalyst (M1 catalyst)
[Preparation of organically modified clay]
Into a 1 L flask, put 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and methyl dioleylamine (Lion Corporation (trade name) Armin M2O). ) 63.8 g (120 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of metallocene catalyst]
After a 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, 25.0 g of the organic modified clay obtained in [Preparation of organic modified clay] and 108 mL of hexane were added, and then isopropylidene (cyclopentadienyl) ( 0.545 g (1 mmol) of 2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and 190 mL (100 mmol) of 15% triisobutylaluminum hexane solution were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and 200 ml of hexane was added to obtain a metallocene catalyst (M1 catalyst) (solid weight: 10 wt%).

Catalyst preparation example 2: metallocene catalyst (M2 catalyst)
[Preparation of organically modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of metallocene catalyst]
Using the organically modified clay obtained in [Preparation of organically modified clay], diphenylmethylene (cyclohexane) was used instead of isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride. Preparation was performed in the same manner as in Catalyst Preparation Example 1 [Preparation of metallocene catalyst] except that 0.669 g (1 mmol) of pentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was used. And a metallocene catalyst (M2 catalyst) was obtained (solid weight: 10 wt%).

Catalyst Preparation Example 3: Metallocene catalyst (M3 catalyst)
[Preparation of metallocene catalyst]
Using the organically modified clay obtained in Catalyst Preparation Example 2 [Preparation of Organically Modified Clay], instead of isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenyl was used. Except that 0.719 g (1 mmol) of methylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was used, the same method as in Preparation Example 1 [Preparation of metallocene catalyst] was used. Preparation was performed to obtain a metallocene catalyst (M3 catalyst) (solid weight: 10 wt%).

Catalyst preparation example 4: Ziegler-Natta catalyst (Z1 catalyst)
In a 10 l stainless steel autoclave equipped with a stirrer, 108.2 g (1.80 mol) of isopropanol and 134.6 g (1.82 mol) of n-butanol were placed, and 2.0 g of iodine and 40 g of metal magnesium powder ( 1.65 mol) and 224.1 g (0.66 mol) of titanium tetrabutoxide, 2.0 liters of hexane were added, and the temperature was raised to 80 ° C., and the generated hydrogen gas was removed under a nitrogen seal. Stir for 1 hour. Subsequently, the temperature was raised to 120 ° C. and the reaction was performed for 1 hour to obtain a uniform solution containing Mg and Ti. The internal temperature of the autoclave was kept at 45 ° C., and 1.32 kg (3.3 mol) of a 30% hexane solution of diethylaluminum chloride was added over 1 hour. After all was added, the mixture was stirred at 60 ° C. for 1 hour. After cooling to 45 ° C., 2.81 kg (9.1 mol) of a 50% hexane solution of isobutylaluminum dichloride was added over 2 hours. After everything was added, the mixture was stirred at 70 ° C. for 1 hour to obtain 287.4 g of a Ziegler-Natta catalyst (B-1) having a Ti content of 11 wt%. The obtained catalyst (Z1 catalyst) was used in the next polymerization step as a hexane slurry after removing unreacted substances and by-products remaining using hexane.

Catalyst preparation example 5: metallocene catalyst (M4 catalyst)
[Preparation of metallocene catalyst]
To a 500 mL flask, 10.5 g of silica (Davison 948, baked under reduced pressure at 200 ° C. for 5 hours) and 200 mL of toluene were added to form a suspension. Thereto was added 66 mL of a toluene solution of methylaluminoxane (2.39 M), and the mixture was stirred at room temperature for 1 hour.

  To the above contact product slurry, 0.335 g (0.5 mmol) of diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added, and the mixture was stirred at room temperature for 1 hour. A catalyst (M4 catalyst) was obtained.

Example 1
[Production of ethylene polymer A]
The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 5 liters was sufficiently replaced with nitrogen, 3 liters of hexane, 3.3 mL of a 15% triisobutylaluminum hexane solution (1.75 mmol), and the metallocene catalyst prepared in Catalyst Preparation Example 1 ( M1 catalyst) 763 mg (solid content 76.3 mg) was charged, and the internal temperature was adjusted to 85 ° C. After adjusting the autoclave internal pressure to 0.1 MPa with nitrogen, polymerization was started by adding an ethylene / hydrogen mixed gas (containing 1,500 ppm of hydrogen) until the autoclave internal pressure reached 1.0 MPa. During the polymerization, an ethylene / hydrogen mixed gas (containing 1,500 ppm of hydrogen) was continuously introduced so that the internal pressure of the autoclave was maintained at 1.0 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 306 g of ethylene polymer A was obtained. The intrinsic viscosity ([η] _A ) of the obtained ethylene polymer was 0.43 dl / g, and the density was 979.8 kg / m ³ .
[Production of ethylene polymer B]
The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 5 liters was sufficiently replaced with nitrogen, 3 liters of hexane, 3.3 mL of a 15% triisobutylaluminum hexane solution (1.75 mmol), 11.9 g of 1-butene and catalyst preparation examples 299 mg (solid content 29.9 mg) of the metallocene catalyst (M3 catalyst) prepared in 3 was charged, and the internal temperature was adjusted to 70 ° C. After adjusting the autoclave internal pressure to 0.1 MPa with nitrogen, polymerization was started by adding an ethylene / hydrogen mixed gas (containing 1,200 ppm of hydrogen) until the autoclave internal pressure reached 1.0 MPa. During the polymerization, an ethylene / hydrogen mixed gas (containing 1,200 ppm of hydrogen) was continuously introduced so that the internal pressure of the autoclave was maintained at 1.0 MPa. The polymerization temperature was controlled at 70 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 101 g of ethylene polymer B was obtained. The obtained ethylene-based polymer had an intrinsic viscosity ([η] _B ) of 4.23 dl / g, a density of 922.3 kg / m ³ , and a molecular weight distribution (Mw / Mn) of 6.0.
[Preparation of polyethylene resin composition]
The ethylene polymer A produced in [Production of ethylene polymer A] and the ethylene polymer B produced in [Production of ethylene polymer B] are blended at 50/50 (wt / wt). Then, to the powder of the obtained ethylene-based polymer composition, Irganox 1010 (manufactured by Ciba Specialty Chemicals: trade name) 1000 ppm, Irgafos 168 (manufactured by Ciba Specialty Chemicals: trade name) 1000 ppm, and calcium stearate 1500 ppm After compounding and premixing, melt kneading was performed using a twin screw extruder (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a screw speed of 20 rpm and a barrel set temperature of 220 ° C. to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.06 g / 10 min and a density of 951.3 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe is produced by the method described in <Pipe molding> above, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test are measured. did. Table 1 shows the characteristic values of the polyethylene pipe.

Example 2
[Preparation of polyethylene resin composition]
Melt-kneading was carried out in the same manner as in Example 1 [Preparation of polyethylene resin composition] except that ethylene polymer A and ethylene polymer B were blended at 47.5 / 52.5 (wt / wt). A polyethylene resin pellet was obtained. The obtained pellet had an MFR of 0.05 g / 10 min and a density of 949.9 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Example 3
[Production of ethylene polymer A]
The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 10 liters was sufficiently replaced with nitrogen, 6.0 liters of hexane was charged, and the internal temperature was adjusted to 80 ° C. Thereafter, 11 mL (5.78 mmol) of a 15% triisobutylaluminum hexane solution and a slurry containing 50 mg of a solid content of Ziegler-Natta catalyst (Z1 catalyst) obtained in Catalyst Preparation Example 4 were sequentially added. After adjusting the autoclave internal pressure to 0.1 MPa, 1.54 MPa of hydrogen was added, and then polymerization was performed for 90 minutes while ethylene was continuously added so that the autoclave internal pressure became 2.1 MPa. After completion of the polymerization, the mixture was cooled to room temperature, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, an ethylene polymer A was obtained. The intrinsic viscosity ([η] _A ) of the obtained ethylene polymer was 0.54 dl / g, and the density was 974.6 kg / m ³ .
[Production of ethylene polymer B]
Example 1 [Ethylene polymer B] except that 244 mg (24.4 mg solid content) of the metallocene catalyst (M2 catalyst) prepared in Catalyst Preparation Example 2 was charged and an ethylene / hydrogen mixed gas (containing 680 ppm of hydrogen) was used. The production was carried out in the same manner as in the above, to obtain 131 g of an ethylene polymer B. The obtained ethylene-based polymer had an intrinsic viscosity ([η] _B ) of 4.66 dl / g, a density of 917.2 kg / m ³ , and a molecular weight distribution (Mw / Mn) of 4.0.
[Preparation of polyethylene resin composition]
65/35 (wt / wt) of the ethylene polymer A produced in Example 3 [Production of ethylene polymer A] and the ethylene polymer B produced in Example 3 [production of ethylene polymer B] Except for blending, melt kneading was carried out in the same manner as in Example 1 [Preparation of polyethylene resin composition] to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.09 g / 10 min and a density of 954.2 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Example 4
[Production of ethylene polymer A]
Except having added hydrogen 1.9MPa, it manufactured by the method similar to Example 3 [manufacturing ethylene-based polymer A], and obtained ethylene-based polymer A. The intrinsic viscosity ([η] _A ) of the obtained ethylene polymer was 0.42 dl / g, and the density was 976.3 kg / m ³ .
[Preparation of polyethylene resin composition]
Example 1 [Polyethylene resin composition] except that the ethylene polymer A and the ethylene polymer B produced in Example 3 [Production of ethylene polymer B] were blended at 65/35 (wt / wt). Melt-kneading was performed in the same manner as in [Preparation of product] to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.09 g / 10 min and a density of 955.9 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Example 5
[Preparation of polyethylene resin composition]
The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 5 liters was sufficiently replaced with nitrogen, and 3 liters of hexane, 3.3 mL (1.75 mmol) of 15% triisobutylaluminum hexane solution and the metallocene catalyst prepared in Catalyst Preparation Example 2 ( M2 catalyst) 763 mg (solid content 76.3 mg) was charged, and the internal temperature was adjusted to 85 ° C. After adjusting the autoclave internal pressure to 0.1 MPa with nitrogen, polymerization was started by adding an ethylene / hydrogen mixed gas (containing 1,500 ppm of hydrogen) until the autoclave internal pressure reached 1.0 MPa. During the polymerization, an ethylene / hydrogen mixed gas (containing 1,500 ppm of hydrogen) was continuously introduced so that the internal pressure of the autoclave was maintained at 1.0 MPa. The polymerization temperature was controlled at 85 ° C. 90 minutes after the start of polymerization, the internal pressure of the autoclave was released to 0 MPa. Furthermore, the operation of adjusting the internal pressure of the autoclave to 0.5 MPa with nitrogen and then releasing the pressure to 0 MPa was repeated three times. The intrinsic viscosity ([η] _A ) of the ethylene polymer A produced by the first stage polymerization was 0.47 dl / g, and the density was 977.9 kg / m ³ . Subsequently, 11.9 g of 1-butene was charged into the autoclave and the internal temperature was adjusted to 70 ° C. After adjusting the autoclave internal pressure to 0.1 MPa with nitrogen, polymerization was started by adding an ethylene / hydrogen mixed gas (containing 1,200 ppm of hydrogen) until the autoclave internal pressure reached 1.0 MPa. During the polymerization, an ethylene / hydrogen mixed gas (containing 1,200 ppm of hydrogen) was continuously introduced so that the internal pressure of the autoclave was maintained at 1.0 MPa. The polymerization temperature was controlled at 70 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, an ethylene polymer composition was obtained. The powder of the obtained ethylene polymer composition is blended with 1000 ppm of Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals), 1000 ppm of Irgaphos 168 (trade name, manufactured by Ciba Specialty Chemicals), and 1500 ppm of calcium stearate. Then, after premixing, melt kneading was performed using a twin screw extruder (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a screw rotation speed of 20 rpm and a barrel set temperature of 220 ° C. to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.08 g / 10 min and a density of 950.6 kg / m ³ (the intrinsic viscosity ([η] _B ) of the ethylene-based polymer B obtained by the second-stage polymerization was 3. 86 dl / g, density was estimated at 923.3 kg / m ³ ). The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Example 6
[Preparation of polyethylene resin composition]
Melting and kneading was carried out in the same manner as in Example 1 [Preparation of polyethylene resin composition], except that ethylene polymer A and ethylene polymer B were blended at 40.0 / 60.0 (wt / wt). A polyethylene resin pellet was obtained. The obtained pellet had an MFR of 0.03 g / 10 min and a density of 945.3 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Example 7
[Production of ethylene polymer A]
Except having added hydrogen 1.9MPa, it manufactured by the method similar to Example 3 [manufacturing ethylene-based polymer A], and obtained ethylene-based polymer A. The intrinsic viscosity ([η] _A ) of the obtained ethylene polymer was 0.42 dl / g, and the density was 976.3 kg / m ³ .
[Preparation of polyethylene resin composition]
Example 1 [Polyethylene resin composition] except that the ethylene polymer A and the ethylene polymer B produced in Example 3 [Production of ethylene polymer B] were blended at 70/30 (wt / wt). Melt-kneading was performed in the same manner as in [Preparation of product] to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.22 g / 10 min and a density of 957.8 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Comparative Example 1
Ziegler-Natta catalyst (Z1 catalyst) obtained by the method of Catalyst Preparation Example 4, 45 kg / hr of dehydrated and purified hexane, 32 mmol / hr of triisobutylaluminum as an organoaluminum compound, in a first stage polymerization vessel having a polymerization internal volume of 370 liters Was continuously fed at a rate of 1.80 g / hr of the solid component, and ethylene was fed at a rate of 25 kg / hr at 85 ° C. while discharging the contents of the polymerization vessel at the required rate, The first-stage polymerization was continuously carried out in a full liquid state under the conditions of a hydrogen to ethylene concentration ratio of 0.93 mol / mol, a total pressure of 2.9 MPa, and an average residence time of 3.7 hours. The hexane slurry containing the polymer obtained in the first stage polymerization vessel was flushed with unreacted hydrogen and ethylene in a flash tank. (The intrinsic viscosity ([η] _A ) of the ethylene polymer in the first stage was 0.53 dl / g and the density was 975.1 kg / m ³ ). Introduced, solid catalyst component and alkylaluminum were not added, hexane was fed at 146 kg / hr, and the contents of the polymerization vessel were discharged at the required rate, while ethylene was 25 kg / hr and 1-butene was 8. Supplying at a rate of 0 kg / hr, maintaining an ethylene concentration of 1.0 wt%, a hydrogen to ethylene concentration ratio of 0.018 mol / mol, and a 1-butene to ethylene concentration ratio of 2.90 mol / mol, and a total pressure of 2.0 MPa The second stage polymerization was carried out under the condition of an average residence time of 1.5 hr. The effluent from the second stage polymerizer was flushed with unreacted hydrogen, ethylene and 1-butene in a flash tank, and then separated from the solvent by filtration and dried. The obtained ethylene polymer composition powder was melt-kneaded in the same manner as in Example 1 to obtain polyethylene resin pellets. The pellets obtained had an MFR of 0.10 g / 10 min and a density of 950.0 kg / m ³ (the intrinsic viscosity of the ethylene polymer (ethylene polymer B) polymerized in the second stage polymerization vessel ([ η] _B ) was estimated to be 3.6 dl / g and density was 924.9 kg / m ³ ). Table 1 shows the characteristic values of the polyethylene resin composition.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Comparative Example 2
[Production of ethylene polymer B]
The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 5 liters was sufficiently replaced with nitrogen, 3 liters of hexane, 3.3 mL of a 15% triisobutylaluminum hexane solution (1.75 mmol), 11.9 g of 1-butene and catalyst preparation examples 200 mg of the metallocene catalyst (M4 catalyst) prepared in Step 5 was charged as a solid content, and the internal temperature was adjusted to 70 ° C. After the autoclave internal pressure was adjusted to 0.1 MPa with nitrogen, an ethylene / hydrogen mixed gas (containing 1,000 ppm of hydrogen) was added until the autoclave internal pressure reached 1.0 MPa to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas (containing 1,000 ppm of hydrogen) was continuously introduced so that the internal pressure of the autoclave was maintained at 1.0 MPa. The polymerization temperature was controlled at 70 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 110 g of ethylene polymer B was obtained. The intrinsic viscosity ([η] _B ) of the obtained ethylene polymer was 4.20 dl / g, the density was 922.5 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.8.
[Preparation of polyethylene resin composition]
Example 1 Except that the ethylene polymer A produced in Example 1 [Production of ethylene polymer A] and the ethylene polymer B were blended at 47.5 / 52.5 (wt / wt). Melt kneading was carried out in the same manner as in [Preparation of polyethylene resin composition] to obtain polyethylene resin pellets. The obtained pellet had an MFR of 0.05 g / 10 min and a density of 950.0 kg / m ³ . The characteristic values of the obtained polyethylene resin composition are shown in Table 1.
[Pipe production and measurement of pipe properties]
Using the obtained polyethylene resin, a polyethylene pipe was produced in the same manner as in Example 1, and the tensile yield strength (σ _y ) and the fracture time (t _f ) by the notch tensile creep test were measured. Table 1 shows the characteristic values of the polyethylene pipe.

Claims (5)

(1) Solution viscosity [η] 10 to 90% by weight of an ethylene homopolymer (referred to as ethylene polymer A) having an _A of 0.3 to 2.0 dl / g and a density d _A of 950 kg / m ³ or more ,
Solution viscosity [η] _B produced by a metallocene catalyst containing component (a) metallocene compound, component (b) organically modified clay, and component (c) organoaluminum compound is 1.0 to 6.0 dl / g, density d _B is 910~955kg / ^{m 3,} than the ratio at which the molecular weight distribution of gel permeation chromatography weight average molecular weight measured by (GPC) (Mw) to the number average molecular weight (Mn) (Mw / Mn) is 3 90 to 10% by weight of copolymer of ethylene and α-olefin having 3 to 20 carbon atoms (referred to as ethylene polymer B) (total amount of ethylene polymer A and ethylene polymer B is 100% by weight) (2) The solution viscosity is [η] _B > [η] _A , the density satisfies the relationship d _A > d _B , (3) the density is 935 to 965 kg / m ³ , (4 ) -Flow rate is 0.01~5g / 10min, (5) Tensile Tensile yield strength was determined by the test (sigma _y) and the tensile creep test full notch type, in 2% aqueous surfactant solution, the measurement temperature The fracture time (t _f ) measured at 80 ° C. and a load stress of 5.4 MPa is σ _y ≧ −3.1 log (t _f ) +31.1
A polyethylene resin composition characterized by satisfying the following relationship: Component (a) is represented by the general formula (7)

[Wherein, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkylamino group having 1 to 20 carbon atoms and an alkylsilyl group having 1 to 20 carbon atoms, and R ³ and R ⁴ are each independently represented by the following general formula (12), (13), (14) or (15): Ligand coordinated to M ¹ represented by

(In the formula, each R ⁷ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms R ³ and R ⁴ together with M ¹ form a sandwich structure, and R ⁵ is represented by the general formula (16) or (17).

(In the formula, each R ⁸ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms. It is an alkylsilyl group, M ² is a silicon atom, a germanium atom or a tin atom.), Which acts to crosslink R ³ and R ⁴ , and n is an integer of 1 to 5. The polyethylene resin composition according to claim 1, wherein the polyethylene resin composition is a metallocene compound represented by the formula: Component (b) is a smectite group clay compound represented by the general formula (18)

(In the formula, R ^{9 to} R ¹¹ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. M ³ is a group 15 atom of the periodic table, R ⁹ R ¹⁰ R ¹¹ HM ³⁺ is a monovalent cation, and A ⁻ is a monovalent anion. 2. The polyethylene resin composition according to claim 1, which is an organically modified clay modified with a compound. The α-olefin used for the ethylene-based polymer B is any one of 1-butene, 1-pentene, 1-hexene and 1-octene. Polyethylene resin composition. A pipe comprising the polyethylene resin composition according to claim 1.