JP5829105B2 - Polyethylene resin composition for blow molding and blow molded article comprising the same - Google Patents

Description

  The present invention relates to a polyethylene resin composition for blow molding and a blow molded article comprising the same. More specifically, for example, a polyethylene resin composition for blow molding that can be used for food containers such as detergent bottles, beverage bottles, edible oil bottles, large containers such as drums and industrial cans, fuel containers such as kerosene cans and gasoline tanks, etc. The present invention relates to a product and a blow molded article made of the same.

Conventionally, polyethylene-based resins are excellent in lightness, heat resistance, chemical resistance, flexibility, mechanical strength, etc., so generally food containers such as detergent bottles, beverage bottles, edible oil bottles, drum cans, Widely used in large containers such as industrial cans, fuel containers such as kerosene cans and gasoline tanks. They are manufactured as a blow container by a hollow molding method (blow molding method).
In the hollow molding method, the resin is melted by an extruder and extruded into a cylindrical parison, and the parison is expanded and deformed by blowing a pressurized gas from a blow pin with the extruded parison sandwiched between molds. It cools after shaping into a cavity shape. These hollow molding methods can be widely applied to hollow molded products such as bottles, gasoline tanks with complex shapes, drum cans, and panel-shaped molded products. It is widely used because the molding cost is low.

  When a polyethylene resin blow container is manufactured, blow molding processability of the polyethylene resin is required. When a container is molded using a polyethylene resin having poor blow molding processability, there is a problem that the surface of the container, particularly the inner surface, becomes rough and the molded appearance becomes poor. In order to improve the blow molding processability, it is generally effective to widen the molecular weight distribution and decrease the molecular weight in order to improve fluidity. However, these improved methods have a problem of deterioration of moldability such as drawdown in a large molded product.

  That is, it is necessary to reduce the low molecular weight component contained in the resin itself. However, when the molecular weight distribution of the resin is narrowed to reduce the low molecular weight component, roughening of the surface of the molded product tends to occur. Therefore, in order to improve the rough skin, multistage polymerization is often performed in which another resin having a narrow molecular weight distribution is introduced into the high molecular weight region. However, just adding a high molecular weight component increases the overall molecular weight, resulting in rough skin, and if the overall molecular weight is lowered to match the molecular weight, large blow molding cannot draw down and form. there were.

  For example, a resin composition having a very narrow molecular weight distribution (= weight average molecular weight / number average molecular weight) is disclosed (for example, see Patent Document 1). However, when the melt flow (MFR) is low, the resin composition is severely roughened during extrusion. When the melt flow is high, drawdown becomes remarkable, which makes it difficult to mold a large blow container.

Moreover, the resin composition with narrow molecular weight distribution obtained by using two-stage polymerization is disclosed (for example, refer patent document 2). In this resin composition, the rough skin property at the time of extrusion of the low MFR resin composition suitable for large blow has not been solved yet.
Moreover, the resin composition using a single site catalyst is disclosed (for example, refer patent document 3). However, improvement in rough skin property is not always sufficient, and there is room for improvement in drawdown property in large-sized molded product applications.
The large size here refers to a bottle whose internal capacity is 10L or more.

Japanese Patent Application Laid-Open No. 9-79721 Japanese Patent Laid-Open No. 11-80257 Japanese Patent Laid-Open No. 11-246714

Yamaguchi et al., Polymer, Vol. 42, 2001, p. 8663 L. A. UTRACKI, Toshio Nishi, “Polymer Alloy and Polymer Blend”, Tokyo Kagaku Doujin, 1st Edition, December 6, 1991, p. 75

Therefore, as a result of paying attention to strain hardening, which is one of the indicators of the physical properties of the resin, it was possible to obtain a polyethylene resin composition for blow molding excellent in blow molding processability.
The problem to be solved by the present invention is to provide a polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a polyethylene-based resin composition having specific physical properties, so that the blow-molding polyethylene-based resin composition is excellent in blow molding processability. It was found that this could be adapted to the solution of the above problem, and the present invention was made based on this finding.

That is, this invention relates to the polyethylene-type resin composition for blow molding of the specific resin structure shown below, and a blow container consisting thereof.
[1]
It has a density of 930 to 960 kg / m ³ , 190 ° C., a melt flow rate at a load of 2.16 kg of 0.1 to 2 g / 10 minutes, and has strain hardening in the measurement of elongational viscosity. Polyethylene resin composition for blow molding.
[2]
The polyethylene resin composition for blow molding as described in [1], which satisfies the following requirements 1) to 2).
1) 90-100 mass% of linear polyethylene ((alpha)) and 10-40 mass% of high-pressure-process low density polyethylene ((beta)) are included.
2) The melting point peak of the endothermic curve obtained in the temperature rise measurement by the differential scanning calorimeter is one.
[3]
The linear polyethylene (α) satisfies the following requirements (α-1) to (α-4), and the high-pressure method low-density polyethylene (β) is represented by the following (β-1) to (β-3). The polyethylene resin composition for blow molding as described in [1] or [2], which satisfies the requirement of
(Α-1) An ethylene homopolymer or a copolymer comprising a repeating unit derived from ethylene and a repeating unit derived from one or two or more α-olefins having 3 to 20 carbon atoms.
(Α-2) The density is 935 to 975 kg / m ³ .
(Α-3) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 min.
((Alpha) -4) Mw / Mn calculated | required by the gel permeation chromatography method is 3-7.
(Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mw / Mn is an index representing a molecular weight distribution.)
(Β-1) The density is 910 to 930 kg / m ³ .
(Β-2) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 10 g / 10 min.
(Β-3) Occupation ratio of components having a converted molecular weight of 10 ⁶ or more determined by gel permeation chromatography is 1.5 to 9.0% by mass of the entire high-pressure method low-density polyethylene (β).
[4]
The linear polyethylene (α) comprises (a) a carrier material, (b) an organoaluminum, (c) a transition metal compound having a cyclic η-binding anion ligand, and (d) the cyclic η-binding anion arrangement. It is produced by polymerization using a metallocene-supported catalyst [I] prepared from an activator capable of reacting with a transition metal compound having a ligand to form a complex that exhibits catalytic activity, and a liquid promoter component [II]. The polyethylene-based resin composition for blow molding according to any one of [1] to [3].
[5]
[1] A blow molded article comprising the polyethylene resin composition for blow molding according to any one of [4].
[6]
The blow molded article according to [5], which is a blow container.

  The polyethylene-based resin composition for blow molding of the present invention is excellent in blow molding processability, and the blow container made thereof has a good molded appearance.

It is an example of the plot figure of the extensional viscosity of the polyethylene-type resin composition for blow molding of this invention.

  Hereinafter, the present invention will be specifically described.

The density of the blow molding polyethylene resin composition of the present invention is preferably 930~960kg / ^{m 3,} more preferably from 940~960kg / ^{m 3,} even more preferably at 945~960kg / ^{m 3} . The density of a polyethylene-type resin composition can be measured by the method as described in the below-mentioned Example. The density of a polyethylene-type resin composition can be adjusted with the component to be used, for example, each density and compounding quantity of a linear polyethylene ((alpha)) and a high pressure method low density polyethylene ((beta)).

If the density of the polyethylene resin composition for blow molding is 930 kg / m ³ or more, when it is used as a blow container, it is excellent in flexibility, mechanical properties and heat stability. If the density of the polyethylene resin composition for blow molding is 960 kg / m ³ or less, a polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molding appearance can be obtained. it can.

  The density of the polyethylene resin composition for blow molding is preferably within the above range in that a blow container excellent in flexibility, mechanical properties and heat stability can be obtained.

The MFR of the polyethylene resin composition for blow molding of the present invention is preferably 0.1 to 2.0 g / 10 min at 190 ° C. and a load of 2.16 kg, more preferably 0.1 to 1.5 g / min. 10 minutes, more preferably 0.1 to 1.0 g / 10 minutes. The MFR of the polyethylene resin composition for blow molding can be measured by the method described in Examples described later. The MFR of the polyethylene resin composition for blow molding can be adjusted by the components used, for example, the MFR and the blending amount of each of linear polyethylene (α) and high-pressure low-density polyethylene (β).
When the MFR of the polyethylene-based resin composition for blow molding is 0.1 g / 10 min or more and 2.0 g / 10 min or less, the blow container is excellent in blow molding processability and the molded appearance is also good.
The polyethylene-based resin composition for blow molding of the present invention has strain-hardening properties in the measurement of elongational viscosity.
Although melt tension is improved by increasing the molecular weight of the resin (decreasing the melt flow rate), conventional polyethylene resins do not exhibit strain hardening in uniaxial elongational flow, and both are regarded as the same. Can not. In the blow molding, the inventors of the present invention have a rapid increase in viscosity accompanying the deformation of the resin, so-called strain hardening phenomenon.
That is, the present inventors have found that the strain curability obtained from the measurement of the extensional viscosity is effective as one index of the resin blow molding processability. This strain hardening property is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is generally affected by the amount of branching and the length of the branched chain. Accordingly, the longer the amount of branching and the length of branching, the greater the strain hardening property.
Here, regarding the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. Details of the measuring method and measuring instrument are described in Non-Patent Document 2, for example. Although described, preferred measuring methods and measuring instruments include the following.
(Measuring method)
Equipment: ARES manufactured by TA Instruments
Jig: Ext. Viscosity Fixture (EVF) Elongation Viscosity Measurement Jig Measurement Temperature: 134 ° C
Strain rate: 0.5 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and thickness 0.7 mm is formed by press molding.
(Calculation method)
The elongational viscosity at a strain rate of 0.5 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line, and the sudden rise phenomenon of the extension viscosity ηE is used as an index of strain hardening property. FIG. 1 is an example of a plot of elongational viscosity.

The polyethylene resin composition for blow molding of the present invention is preferably composed of linear polyethylene (α) and high-pressure method low-density polyethylene (β). The blending ratio of the linear polyethylene (α) and the high pressure method low density polyethylene (β) is preferably 90 to 60% by mass of the linear polyethylene (α) and 10 to 40% by mass of the high pressure method low density polyethylene (β). More preferably, the linear polyethylene (α) is 85 to 65% by mass, and the high pressure method low density polyethylene (β) is 15 to 35% by mass, and more preferably, the linear polyethylene (α) is 80 to 70% by mass, the high pressure method. It is 20-30 mass% of low density polyethylene ((beta)).
If the blend amount of the branched high-pressure method low-density polyethylene (β) is 10% by mass or more and 40% by mass or less, the blow-molding polyethylene resin composition excellent in blow molding processability and the molded appearance made thereof are good. Can be obtained.
The melting point peak of the endothermic curve obtained in the temperature rise measurement by the differential scanning calorimeter of the polyethylene resin composition for blow molding of the present invention is preferably one. Thus, it is presumed that the linear polyethylene (α) and the branched high-pressure low-density polyethylene (β) can be made in a compatible state, and the crystal state of both can be suppressed from phase separation. For this reason, the polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance can be obtained.
The endothermic curve in the temperature rise measurement of the polyethylene resin composition can be obtained by the same method as the measurement method for linear polyethylene (α) described later. Usually, linear polyethylene (α) and high-pressure low-density polyethylene (β) have low compatibility, but by using linear polyethylene (α) with a narrow molecular weight distribution, a resin composition having a single melting point peak is obtained. Can be obtained. By using linear polyethylene (α) having a narrow molecular weight distribution, the compatibility between the two is considered to be enhanced.

  Polyethylene resin compositions having such characteristics have, for example, a large proportion of linear polyethylene (α) having a narrow molecular weight distribution (Mw / Mn) and a high molecular weight component required by gel permeation chromatography. It can be obtained by blending high-pressure low-density polyethylene (β) having more branched side chains. When a conventional general Ziegler catalyst type linear polyethylene and a high pressure method low density polyethylene are mixed, both are incompatible, and the crystal state of both phase separates. It is difficult to obtain a polyethylene resin composition for blow molding that has excellent strain hardening properties.

(Linear polyethylene (α))
The linear polyethylene (α) preferably used in the polyethylene resin composition for blow molding of the present invention is an ethylene homopolymer or a repeating unit derived from ethylene and one or two or more kinds of α- having 3 to 20 carbon atoms. A copolymer comprising repeating units derived from olefins is preferred. “Linear” polyethylene is a concept that excludes conventional high-pressure low-density polyethylene, and is a concept that includes any other polyethylene.

  Examples of the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. 1-octadecene, 1-eicocene, 3-methyl-1-butene, 4-methyl-1-pentene, 6-methyl-1-heptene and the like. As the α-olefin, 1-butene, 1-hexene and 1-octene are preferable because they are generally easily available, and 1-butene is preferable in consideration of the polymerization process.

  The copolymer may be a copolymer of ethylene and one kind of α-olefin, or may be a copolymer of ethylene and an α-olefin obtained by combining two or more kinds. The linear polyethylene (α) may be a copolymer obtained by dry blending or melt blending a copolymer of ethylene and α-olefin and a copolymer of ethylene and another α-olefin at an arbitrary ratio. Good.

The density of the linear polyethylene (α) used in the present embodiment is preferably 935 to 975 kg / m ³ . The density of the linear polyethylene (α) is more preferably 940 to 965 kg / m ³ , and still more preferably 945 to 960 kg / m ³ .

When the density of the linear polyethylene (α) is 935 kg / m ³ or more, when it is used as a blow container of a polyethylene resin composition for blow molding, it is excellent in flexibility, mechanical properties and heat stability. If the density of the linear polyethylene (α) is 975 kg / m ³ or less, when it is used as a blow container of a polyethylene resin composition for blow molding, it has excellent flexibility, mechanical properties and heat stability and good blow Molding processability is also obtained.
The density of the linear polyethylene (α) is such that when it is made into a blow container of a polyethylene resin composition for blow molding, it has excellent flexibility, mechanical properties and heat stability, and good blow moldability is obtained. Within the above range, it is preferable.
In the present embodiment, the density can be measured by the method described in the following examples. Moreover, the density of the linear polyethylene (α) in the resin composition can be measured by fractionating the linear polyethylene by a method such as a cross fractionation chromatography method (CFC method).

  The MFR of the linear polyethylene (α) used in the present embodiment is preferably 0.1 to 2.0 g / 10 min at 190 ° C. and a 2.16 kg load. MFR of linear polyethylene ((alpha)) becomes like this. More preferably, it is 0.1-1.5 g / 10min, More preferably, it is 0.1-1.0 g / 10min.

When the MFR of the linear polyethylene (α) is 0.1 g / 10 min or more and 2.0 g / 10 min or less, the blow molding process of the blow-molded polyethylene resin composition is excellent and the molding appearance is also good. It is good.
In the present embodiment, MFR can be measured by the method described in the following examples. Moreover, MFR of linear polyethylene ((alpha)) in a resin composition can be calculated | required from the compounding ratio of MFR and linear polyethylene of a resin composition.

  In the gel permeation chromatography method, the molecular weight distribution (Mw / Mn) of the linear polyethylene (α) used in the present embodiment is preferably 3-7, more preferably 3-6. It is. In the case of linear polyethylene obtained using a Ziegler catalyst which is a general catalyst, the molecular weight distribution is at least about 8-9, but by using a specific catalyst described later, a linear polyethylene having a narrow molecular weight distribution. Can be obtained.

  If the molecular weight distribution of the linear polyethylene (α) is within the above range, the polyethylene resin composition for blow molding excellent in blow molding processability and the molded appearance comprising the same due to the uniformity of the molecular weight. A good blow container can be obtained.

  In particular, if the molecular weight distribution of the linear polyethylene (α) is 7 or less, a conventional general Ziegler-Natta catalyst is used in a blend of the linear polyethylene (α) and the high pressure method low density polyethylene (β). Unlike the case of the polymerized ethylene homopolymer or the copolymer of ethylene and α-olefin, the linear polyethylene (α) and the high pressure method low density polyethylene (β) may be in a good compatible state. It is presumed that it is possible to suppress phase separation of both crystal states. For this reason, the polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance can be obtained.

  In the present embodiment, the molecular weight distribution can be determined by gel permeation chromatography, and more specifically can be measured by the method described in the following examples. In addition, the molecular weight distribution of the linear polyethylene (α) in the polyethylene resin composition can be measured by a method such as a cross-fractionation chromatography method (CFC method).

The linear polyethylene (α) preferably used in the present invention is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin, and preferably has a molecular weight distribution (Mw / Mn) of 3 to 7. And narrow. For this reason, it is guessed that the subject of the present invention is achieved when the molecular weight becomes uniform.
The crystallization temperature, which is the peak of the endothermic curve and the peak of the exothermic curve of the linear polyethylene (α) preferably used in the present invention, can be determined in the temperature rise measurement and temperature drop measurement using a differential scanning calorimeter, respectively.
It is preferable that the melting point peak of the endothermic curve obtained in the temperature rising measurement of the linear polyethylene (α) with a differential scanning calorimeter is one. Thus, it is presumed that the linear polyethylene (α) and the high-pressure method low-density polyethylene (β) can be made in a compatible state and the crystal state of both can be prevented from phase separation. For this reason, the polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance can be obtained.
The crystallization temperature which is the peak of the exothermic curve obtained in the temperature drop measurement of the linear polyethylene (α) by a differential scanning calorimeter is 110 ° C to 130 ° C, preferably 115 ° C to 125 ° C. . When the crystallization temperature is 110 ° C. or more and the crystallization temperature is 130 ° C. or less, a blow molding polyethylene resin composition excellent in blow molding processability and a blow container having a good molding appearance are obtained. Can do.
The differential scanning calorimeter can be measured using a differential scanning calorimeter (Pyris 1 type DSC device manufactured by Perkin Elmer) under the following conditions. 1) About 5 mg of a polymer sample is packed in an aluminum pan, heated to 200 ° C. at 200 ° C./min, and held at 200 ° C. for 5 minutes. 2) Next, the temperature is lowered from 200 ° C. to 50 ° C. at a temperature lowering rate of 10 ° C./min, and held for 5 minutes after the temperature lowering is completed. 3) Next, the temperature is increased from 50 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. From the exothermic curve observed in the process of 2), the maximum temperature at the exothermic peak position can be obtained as the crystallization temperature (° C.). Further, the maximum temperature at the melting peak position can be determined as the melting point peak (° C.) from the endothermic curve observed in the process of 3).

The production method of the linear polyethylene (α) can be produced by the method described below as a first preferred embodiment.
The linear polyethylene (α) obtained by this production method is characterized by a narrow Mw / Mn and molecular weight distribution obtained by gel permeation chromatography.
A preferred method for producing the linear polyethylene (α) is a method of producing a polyolefin by single-stage polymerization of an α-olefin, and the catalyst used for the polymerization is a solid catalyst [A] and an organometallic compound [ B], and the solid catalyst [A] is represented by an organic magnesium compound (a-1) that is soluble in an inert hydrocarbon solvent represented by the following general formula (1) and the following general formula (2): The carrier (A-1) prepared by the reaction with the chlorinating agent (a-2) is reacted with alcohol (A-2), and then an organometallic compound represented by the following general formula (3) ( A-3) is reacted, and then prepared by supporting a titanium compound (A-4) represented by the following general formula (4). The organometallic compound [B] is represented by the following general formula ( 5) and the following general formula (6) A polyolefin production method, which belongs to the group consisting of organomagnesium compounds that are soluble in the inert hydrocarbon solvent represented.
(M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c- (1)
(In the formula, M ¹ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ , R ² and R ³ are each a carbon number. 2 or more and 20 or less, and α, β, a, b and c are real numbers satisfying the following relationship: 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 <c, 0 <a + b, 0 <c / (α + β) ≦ 2, kα + 2β = a + b + c (where k is the valence of M ¹ ))
_{^{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
_{^{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )
_{^{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)
R ¹⁴ _(3-j) AlQ ′ _j − (5)
(Wherein R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, Q ′ is a group belonging to the group consisting of a hydrogen atom, a halogen atom, and OR ¹⁵ , and R ¹⁵ is a group having 1 to 20 carbon atoms. And j is a real number of 0 or more and 2 or less)
(M ³ ) _γ (Mg) _δ (R ¹⁵ ) _m (R ¹⁶ ) _n- (6)
(In the formula, M ³ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹⁵ and R ¹⁶ each have 2 to 20 carbon atoms. The following hydrocarbon groups, γ, δ, m, and n are real numbers that satisfy the following relationship: 0 ≦ γ, 0 <δ, 0 ≦ k, 0 ≦ m, pγ + 2δ = m + n (where p is M Valence of ³ ))

  Next, the solid catalyst [A] will be described.

An organic magnesium compound (a-1) in which the solid catalyst [A] is soluble in an inert hydrocarbon solvent represented by the following general formula (1) and a chlorinating agent represented by the following general formula (2) ( The carrier (A-1) prepared by the reaction with a-2) is reacted with alcohol (A-2), and then an organoaluminum compound (A-3) represented by the following general formula (3) It is prepared by reacting and then supporting a titanium compound (A-4) represented by the following general formula (4).
(M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c- (1)
(In the formula, M ¹ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ , R ² and R ³ are each a carbon number. 2 or more and 20 or less, and α, β, a, b and c are real numbers satisfying the following relationship: 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 <c, 0 <a + b, 0 <c / (α + β) ≦ 2, kα + 2β = a + b + c (where k is the valence of M ¹ ))
_{^{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
_{^{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )
_{^{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)

  Next, the inert hydrocarbon solvent will be described. The inert hydrocarbon solvent is an aliphatic hydrocarbon compound such as pentane, hexane or heptane, an aromatic hydrocarbon compound such as benzene or toluene, or an alicyclic hydrocarbon compound such as cyclohexane or methylcyclohexane. A hydrocarbon is preferred.

  Next, the organomagnesium compound that is soluble in the inert hydrocarbon solvent represented by the general formula (1) will be described. This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds It is. The relational expression kα + 2β = a + b + c of the symbols α, β, a, b, c indicates the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (1), the hydrocarbon group represented by R ¹ to R ² is an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, Examples include decyl, cyclohexyl, and phenyl groups, and preferably R ¹ to R ² are alkyl groups. When α> 0, as the metal atom M ¹ , a metal element belonging to Groups I to III of the periodic table can be used, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. However, aluminum, boron, beryllium, and zinc are particularly preferable.

The ratio β / α of magnesium to the metal atom M ¹ can be arbitrarily set, but is preferably in the range of 0.1 to 30, particularly 0.5 to 10. Further, when a certain organomagnesium compound in which α = 0 is used, for example, when R ¹ is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound is also used in the present invention. Gives favorable results. In the general formula (M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c , R ¹ and R ² when α = 0 are the following three groups (1), It is recommended that it is any one group of (2) and (3).

(1) At least one of R ¹ and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ¹ and R ² are both 4 to 6 carbon atoms, At least one is a secondary or tertiary alkyl group.
(2) R ¹ and R ² are alkyl groups having different carbon atoms, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ¹ is an alkyl having 4 or more carbon atoms. Be a group.
(3) At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group that becomes 12 or more when the number of carbon atoms contained in R ¹ and R ² is added. .

  These groups are specifically shown below. As the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1), 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2 , 2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like are used, and 1-methylpropyl group is particularly preferable. Next, in (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, propyl and the like, and an ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include butyl, pentyl, hexyl, heptyl, octyl group and the like, and butyl and hexyl groups are particularly preferable.

  Furthermore, examples of the hydrocarbon group having 6 or more carbon atoms in (3) include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable. In general, an increase in the number of carbon atoms contained in an alkyl group facilitates dissolution in an inert hydrocarbon solvent. However, the use of an unnecessarily long alkyl group is not preferred in terms of handling because the solution viscosity increases. The organomagnesium compound is used as an inert hydrocarbon solution, but it can be used as long as a trace amount of Lewis basic compounds such as ethers, esters, and amines are contained or remain in the solution.

Next, the alkoxy group (OR ³ ) will be described. The hydrocarbon group represented by R ³ is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, Examples include 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl groups, and the like. Butyl, 1-methylpropyl, 2 -Methylpentyl and 2-ethylhexyl groups are particularly preferred.

These organomagnesium compounds include an organomagnesium compound belonging to the group consisting of the general formulas R ¹ MgX and R ¹ ₂ Mg (R ¹ is as defined above, X is a halogen), and the general formula M ¹ R ² _k And an organometallic compound belonging to the group consisting of M ¹ R ² _(k-1) H (M ¹ , R ² , k are as defined above) in an inert hydrocarbon solvent at room temperature to 150 ° C. An alkoxymagnesium compound having a hydrocarbon group represented by R ³ that is soluble in an alcohol having an hydrocarbon group represented by R ³ or an inert hydrocarbon solvent, if necessary, and the like. It is synthesized by the method of reacting.

  Among these, when reacting an organomagnesium compound soluble in an inert hydrocarbon solvent with an alcohol, the order of the reaction is such that the alcohol is added to the organomagnesium compound, or the organomagnesium compound is added to the alcohol. Any method can be used, or a method of adding both at the same time. In the present invention, the reaction ratio between the organomagnesium compound soluble in the inert hydrocarbon solvent and the alcohol is not particularly limited, but as a result of the reaction, the alkoxy group-containing organomagnesium compound in the resulting alkoxy group-containing organomagnesium compound contains all of the alkoxy groups. The range of the molar composition ratio c / (α + β) is 0 ≦ c / (α + β) ≦ 2, and 0 ≦ c / (α + β) <1 is particularly preferable.

Next, the chlorinating agent preferably used will be described.
The chlorinating agent preferably used when synthesizing (A-1) is represented by the following general formula (2), and at least one is a silicon chloride compound having a Si—H bond.
^{_{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
In the above formula (2), the hydrocarbon group represented by R ⁴ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. For example, methyl, ethyl, propyl, 1- Examples thereof include methylethyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group, etc., preferably an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom such as methyl, ethyl, propyl, 1-methylethyl group, etc. An alkyl group of ˜3 is particularly preferred. D and e are 1 or more real numbers satisfying the relationship of 2 ≦ d + e ≦ 4, and it is particularly preferable that e is 2 or more.

These compounds include HSiCl ₃ , HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl ₂ C ₃ H ₇ , HSiCl ₂ (1-CH ₃ C ₂ H ₅ ), HSiCl ₂ C ₄ H ₉ , HSiCl _{2 C 6 H 5, HSiCl 2 (} 4-Cl-C 6 H 4), HSiCl 2 CH = CH 2, HSiCl 2 CH 2 C 6 H 5, HSiCl 2 (1-C 10 H 7), HSiCl 2 CH 2 CH = CH ₂ , H ₂ SiClCH ₃ , H ₂ SiClC ₂ H ₅ , HSiCl (CH ₃ ) ₂ , HSiCl (C ₂ H ₅ ) ₂ , HSiClCH ₃ (1-CH ₃ C ₂ H ₅ ), HSiClCH ₃ (C _{6 H 5), HSiCl (C 6} H 5) 2 and the like, selected from these compounds or these compounds two or more mixed Silicon chloride compounds are used consisting of an object. As the silicon chloride compound, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, and ethyldichlorosilane are preferable, and trichlorosilane and monomethyldichlorosilane are particularly preferable.

  Next, the reaction between the organomagnesium compound and the chlorinating agent that are preferably used will be described. In the reaction of the organomagnesium compound and the chlorinating agent, the chlorinating agent is previously converted into a reaction solvent body, for example, a chlorinated hydrocarbon such as an inert hydrocarbon solvent, 1,2-dichloroethane, o-dichlorobenzene, dichloromethane, or the like. It is preferably used after being diluted with an ether-based medium such as diethyl ether or tetrahydrofuran, or a mixed medium thereof. In particular, in view of the performance of the catalyst, an inert hydrocarbon solvent is preferable. In this case, although there is no restriction | limiting in particular about the temperature of reaction, For progress of reaction, Preferably it implements above the boiling point of the silicon chloride compound used as a chlorinating agent, or 40 degreeC or more. Although there is no restriction | limiting in particular also in the reaction ratio of an organomagnesium compound and a silicon chloride compound, Usually, it is 0.01-100 mol of silicon chloride compounds with respect to 1 mol of organomagnesium compounds, Preferably with respect to 1 mol of organomagnesium compounds, It is the range of 0.1-10 mol of silicon chloride compounds.

  Regarding the reaction method, a method of simultaneous addition in which an organomagnesium compound and a silicon chloride compound are simultaneously introduced into the reactor and a reaction is performed, and after the silicon chloride compound is charged in the reactor in advance, the organomagnesium compound is introduced into the reactor. There is a method, or a method of introducing an organomagnesium compound into the reactor in advance and then introducing a silicon chloride compound into the reactor, but after introducing the silicon chloride compound into the reactor in advance, the organomagnesium compound is introduced into the reactor The method of making it preferable is. The solid component obtained by the above reaction is preferably separated by filtration or decantation, and then sufficiently washed with an inert hydrocarbon solvent to remove unreacted products or by-products.

The reaction between the organomagnesium compound and the silicon chloride compound can also be performed in the presence of a solid. This solid may be either an inorganic solid or an organic solid, but it is preferable to use an inorganic solid. The following are mentioned as an inorganic solid.
(I) Inorganic oxide (ii) Inorganic carbonate, silicate, sulfate (iii) Inorganic hydroxide (iv) Inorganic halide (v) Double salt, solid solution or mixture of (i) to (iv)

Specific examples of the inorganic solid include silica, alumina, silica / alumina, hydrated alumina, magnesia, tria, titania, zirconia, calcium phosphate, barium sulfate, calcium sulfate, magnesium silicate, magnesium / calcium, aluminum silicate [(Mg / Ca ) O · Al ₂ O ₃ · 5SiO ₂ · nH ₂ O], potassium silicate · aluminum [K ₂ O · 3Al ₂ O ₃ · 6SiO ₂ · 2H ₂ O], magnesium iron silicate [(Mg · Fe) ₂ SiO ₄ ], Aluminum silicate [Al ₂ O ₃ · SiO ₂ ], calcium carbonate, magnesium chloride, magnesium iodide, and the like, and particularly preferred are silica, silica / alumina and magnesium chloride. The specific surface area of the inorganic solid is preferably 20 m ² / g or more, particularly preferably 90 m ² / g or more.

  Next, the alcohol (A-2) that is preferably used will be described. As the alcohol (A-2), a saturated or unsaturated alcohol having 1 to 20 carbon atoms is preferable. Such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 1-pentanol, Examples include hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, phenol, cresol, and the like, and linear alcohols having 3 to 8 carbon atoms are particularly preferable. It is also possible to use a mixture of these alcohols.

  Although there is no restriction | limiting in particular in the usage-amount of alcohol (A-2), It is preferable that it is more than 0.05 and 10 or less by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), 0.1 or more 1 or less is more preferable, and 0.2 or more and 0.5 or less are more preferable. When the amount of alcohol (A-2) used is greater than 0.05 in terms of the molar ratio to the magnesium atom contained in the support (A-1), the Si-containing component contained in the catalyst support is efficiently removed. This is preferable because the catalytic properties are improved. Moreover, when the usage-amount of alcohol (A-2) is 10 or less by the molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), an excess alcohol remains in a catalyst, and catalyst characteristics are obtained. This is preferable because the phenomenon of lowering can be suppressed. Furthermore, when the amount of alcohol (A-2) used is 0.2 or more and 0.5 or less in terms of a molar ratio to the magnesium atom contained in the carrier (A-1), the catalyst characteristics are improved. This is preferable because an appropriate amount of alcohol remaining in the catalyst remains in the catalyst. The reaction of the carrier (A-1) and the alcohol (A-2) can be carried out in the presence or absence of an inert hydrocarbon solvent. Although there is no restriction | limiting in particular in the temperature at the time of reaction, It is preferable to implement in 25 to 200 degreeC.

Next, the organometallic compound (A-3) that is preferably used will be described.
This organometallic compound (A-3) is represented by the following general formula (3).
^{_{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )

M ² is a metal atom belonging to Groups I to III of the Periodic Table, and examples thereof include lithium, sodium, potassium, beryllium, magnesium, boron, aluminum, and the like, and magnesium, boron, and aluminum are particularly preferable. The hydrocarbon group represented by R ⁵ is an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group and a phenyl group. Is an alkyl group.

Q represents a group belonging to the group consisting of OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R ¹¹ , SR ¹² and halogen, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² Is a hydrogen atom or a hydrocarbon group, and Q is particularly preferably halogen.

  Examples of the organometallic compound (A-3) include methyllithium, butyllithium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, butylmagnesium chloride, butyl Magnesium bromide, butyl magnesium iodide, dibutyl magnesium, dihexyl magnesium, triethyl boron, trimethylaluminum, dimethylaluminum bromide, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, methylaluminum sesquichloride, triethylaluminum, diethylaluminum chloride, diethyl Aluminum bromide, die Rualuminum ethoxide, ethylaluminum dichloride, ethylaluminum sesquichloride, tripropylaluminum, tributylaluminum, tri (2-methylpropyl) aluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Particularly preferred. It is also possible to use a mixture of these compounds.

  Although there is no restriction | limiting in particular in the usage-amount of an organometallic compound (A-3), It is preferable that it is 0.01 times or more and 20 times or less in molar ratio with respect to alcohol (A-2), 0.1 times or more and 10 Or less, more preferably 0.5 times or more and 2.5 times or less. If the amount of the organometallic compound (A-3) used is 0.01 times or more in terms of the molar ratio to the alcohol (A-2), excess alcohol can be efficiently removed, and organic If the usage-amount of a metal compound (A-3) is 20 times or less by the molar ratio with respect to alcohol (A-2), an organometallic compound (A-3) will be an organometallic compound (A-3) in a catalyst manufacturing process. Does not adversely affect the subsequent steps of the reaction. Furthermore, if the amount of the organometallic compound (A-3) used is 0.5 to 2.5 times the molar ratio to the alcohol (A-2), the alcohol necessary for improving the catalyst characteristics Can be left in the catalyst. Moreover, it is preferable that it is 0.01 times or more and 20 times or less by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), and it is still more preferable that they are 0.1 times or more and 10 times or less. Although there is no restriction | limiting in particular about the temperature of reaction, The range which is 25 degreeC or more and 200 degrees C or less and less than the boiling point of a reaction medium is preferable.

Next, the titanium compound (A-4) that is preferably used will be described.
As the titanium compound (A-4), a titanium compound represented by the following general formula (4) is used.
^{_{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)
Examples of the hydrocarbon group represented by R ¹³ include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, and allyl groups, cyclohexyl, and 2-methylcyclohexyl. And alicyclic hydrocarbon groups such as cyclopentyl group and aromatic hydrocarbon groups such as phenyl and naphthyl groups, etc., and aliphatic hydrocarbon groups are preferred. Examples of the halogen atom represented by X include chlorine, bromine and iodine, with chlorine being preferred. Specifically, titanium tetrachloride is preferable. Two or more kinds of titanium compounds (A-4) selected from the above can be mixed and used.

  Although there is no restriction | limiting in particular in the usage-amount of a titanium compound (A-4), About the load with respect to a support | carrier (A-1), 0.01 or more 20 by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1). The following is preferable, and 0.05 or more and 10 or less are particularly preferable. If the amount of the titanium compound (A-4) supported on the carrier (A-1) is too small, the polymerization activity per catalyst is low, and if it is too large, the polymerization activity per titanium tends to be low. If the amount of the titanium compound (A-4) supported on the carrier (A-1) is 0.01 or more in terms of the molar ratio to the magnesium atom contained in the carrier (A-1), the polymerization activity per catalyst is sufficiently high. If it is high and 20 or less, the polymerization activity per titanium is sufficiently high. Although there is no restriction | limiting in particular about the reaction temperature in the case of carrying | supporting, It is preferable to carry out in 25 to 150 degreeC.

When carrying | supporting a titanium compound (A-4), it is preferable to carry | support by making a titanium compound (A-4) and an organometallic compound (A-5) react. This organometallic compound (A-5) is a compound represented by the aforementioned general formula (3), and may be the same as or different from the aforementioned organometallic compound (A-3).
^{_{M 2 R 5 f Q (h}} -f) - (3)

  The order of the reaction between (A-4) and (A-5) is not particularly limited, and (A-5) is added following (A-4). Following (A-5), (A- Any method of adding 4) and adding (A-4) and (A-5) simultaneously is possible, and it is preferable to add (A-5) following (A-4). The molar ratio of (A-5) to (A-4) is preferably 0.1 to 10, particularly preferably 0.5 to 5. The reaction between (A-2) and (A-5) is carried out in an inert hydrocarbon solvent, but it is preferable to use an aliphatic hydrocarbon solvent such as hexane or heptane. Although there is no restriction | limiting in particular about the temperature of reaction, The range which is 25 degreeC or more and 200 degrees C or less and less than the boiling point of a reaction medium is preferable.

  Next, the organometallic compound [B] that is preferably used will be described. The organometallic compound [B] is preferably an organoaluminum compound represented by the following general formula (5) or a specific organomagnesium compound represented by the following general formula (6).

The organoaluminum compound preferably used is represented by the following general formula (5).
R ¹⁴ _(3-j) AlQ ′ _j − (5)
(Wherein R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, Q ′ is a group belonging to the group consisting of a hydrogen atom, a halogen atom, and OR ¹⁵ , and R ¹⁵ is a group having 1 to 20 carbon atoms. And j is a real number of 0 or more and 2 or less)
Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, 2-methylpropyl, pentyl, 3-methylbutyl, hexyl, octyl, decyl, phenyl, tolyl, and the like. Of these, an ethyl group and a 2-methylpropyl group are particularly preferable. Two or more kinds of these hydrocarbon groups may be contained. h is preferably 0.05 or more and 1.5 or less, and particularly preferably 0.1 or more and 1.2 or less.

Next, the organomagnesium compound is represented by the following general formula (6).
(M ³ ) _γ (Mg) _δ (R ¹⁵ ) _m (R ¹⁶ ) _n- (6)
(In the formula, M ³ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹⁵ and R ¹⁶ each have 2 to 20 carbon atoms. The following hydrocarbon groups, γ, δ, m, and n are real numbers that satisfy the following relationship: 0 ≦ γ, 0 <δ, 0 ≦ k, 0 ≦ m, pγ + 2δ = m + n (where p is M Valence of ³ ))

  This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds It is. The relationship between the symbols γ, δ, m and n, pγ + 2δ = m + n, indicates the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (6), the hydrocarbon group represented by R ¹⁵ and R ¹⁶ is an alkyl group, a cycloalkyl group, or an aryl group. For example, methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, decyl, cyclohexyl, phenyl and the like, and preferably ^{R 15} and ^{R 16} alkyl groups. When γ> 0, as the metal atom M ³ , a metal element belonging to Groups I to III of the periodic table can be used, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. However, aluminum, boron, beryllium, and zinc are particularly preferable.

The ratio δ / γ of magnesium to metal atom M ³ is not particularly limited, but is preferably 0.1 or more and 30 or less, more preferably 0.5 or more and 10 or less. In addition, when an organomagnesium compound in which γ = 0 is used, for example, when R ¹⁵ is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound also has preferable results in the present invention. give. In the above general formula (6), when γ = 0, R ¹⁵ and R ¹⁶ are preferably any one of the following three groups (1), (2) and (3): Is done.

(1) At least one of R ¹⁵ and R ¹⁶ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ¹⁵ and R ¹⁶ have 4 to 6 carbon atoms. Yes, at least one of which is a secondary or tertiary alkyl group.
(2) R ¹⁵ and R ¹⁶ are alkyl groups having different carbon atoms, preferably R ¹⁵ is an alkyl group having 2 or 3 carbon atoms, and R ¹⁶ is an alkyl having 4 or more carbon atoms. Be a group.
(3) At least one of R ¹⁵ and R ¹⁶ is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group that becomes 12 or more when the number of carbon atoms contained in R ¹⁵ and R ¹⁶ is added. .

  These groups are specifically shown below. Examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1) include 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like are used, and 1-methylpropyl group is particularly preferable.

  Next, in (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, propyl group and the like, and the ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include butyl, pentyl, hexyl, heptyl, octyl group and the like, and butyl and hexyl groups are particularly preferable.

  Furthermore, examples of the hydrocarbon group having 6 or more carbon atoms in (3) include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable. In general, an increase in the number of carbon atoms contained in an alkyl group facilitates dissolution in an inert hydrocarbon solvent. However, the use of an unnecessarily long alkyl group is not preferred in terms of handling because the solution viscosity increases. The organomagnesium compound is used as an inert hydrocarbon solution, but it can be used as long as a trace amount of Lewis basic compounds such as ethers, esters, and amines are contained or remain in the solution.

These organomagnesium compounds include organomagnesium compounds belonging to the group consisting of general formulas R ¹⁵ MgX and R ¹⁵ ₂ Mg (R ¹⁵ is as defined above, X is halogen), and general formula M ³ R ¹⁶ _k. And an organometallic compound belonging to the group consisting of M ³ R ¹⁶ _(k-1) H (M ³ , R ¹⁶ , k are as defined above) in an inert hydrocarbon solvent at 25 ° C. or higher and 150 ° C. or lower. It is synthesized by the method of reacting between them.

  The catalyst thus obtained is characterized by a high activity per titanium and a very high activity per catalyst, especially for the polymerization of ethylene and the copolymerization of ethylene and an α-olefin having 3 or more carbon atoms.

  As the polymerization solvent, an inert hydrocarbon solvent usually used for slurry polymerization is preferably used. The polymerization temperature is usually from room temperature to 120 ° C., and preferably from 50 ° C. to 100 ° C. The polymerization pressure is usually carried out in the range of normal pressure to 10 MPa. The molecular weight of the resulting polymer can be adjusted by changing the concentration of hydrogen present in the polymerization system, changing the polymerization temperature, or changing the concentration of the organometallic compound [B].

  There is no restriction | limiting in particular in the manufacturing process of polyolefin using the said catalyst, It can apply also to any manufacturing method of the generally used solution method, a high pressure method, a high pressure bulk method, a gas method, and a slurry method. For example, the polymerization pressure is from 0.1 MPa to 200 MPa as the gauge pressure, the polymerization temperature is from 25 ° C. to 250 ° C., and propane, butane, isobutane, hexane, cyclohexane or the like is used as the solvent.

As a second preferred embodiment of the method for producing linear polyethylene (α), the metallocene-supported catalyst [I] is previously brought into contact with hydrogen and then introduced into the polymerization reactor together with the liquid promoter component [II]. Examples thereof include polymerization of ethylene alone or copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms.
The linear polyethylene (α) obtained by this production method has a low Mw / Mn and molecular weight distribution obtained by gel permeation chromatography, as well as a low molecular weight component, unlike the production method described above. Since the oligomer component can be reduced and chlorine is not included in the production method, it is excellent in cleanliness and suitable for blow molded articles for semiconductors, medicines and medical use.

  Various known methods can be used as the polymerization method, such as fluidized bed gas phase polymerization or stirring gas phase polymerization in an inert gas, slurry polymerization in an inert solvent, bulk polymerization using a monomer as a solvent, and the like. Can be mentioned. As the polymerization method, slurry polymerization in an inert solvent is preferable.

(Metallocene supported catalyst [I])
The metallocene-supported catalyst [I] includes (Ia) support material, (Ib) organoaluminum, (Ic) transition metal compound having a cyclic η-bonding anion ligand, and (Id) It is preferable to use a metallocene-supported catalyst prepared from an activator capable of reacting with the transition metal compound having a cyclic η-bonding anion ligand to form a complex that exhibits catalytic activity.

  (Ia) The carrier material may be either an organic carrier or an inorganic carrier.

  Preferred examples of the organic carrier include C2-C20 α-olefin polymers, aromatic unsaturated hydrocarbon polymers, and polar group-containing polymers.

  Examples of the polymer of α-olefin having 2 to 20 carbon atoms include ethylene resin, propylene resin, 1-butene resin, ethylene-propylene copolymer resin, ethylene-1-hexene copolymer resin, propylene-1- Examples include butene copolymer resins and ethylene-1-hexene copolymers.

  Examples of the aromatic unsaturated hydrocarbon polymer include styrene resin and styrene-divinylbenzene copolymer resin.

  Examples of the polar group-containing polymer include acrylic ester resins, methacrylic ester resins, acrylonitrile resins, vinyl chloride resins, amide resins, and carbonate resins.

  Preferred examples of the inorganic carrier include inorganic oxides, inorganic halides, inorganic carbonates, sulfates, nitrates, and hydroxides.

As the inorganic oxide, _{e.g., SiO 2, Al 2 O 3} , MgO, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO, SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO 2 - MgO and SiO ₂ —V ₂ O ₅ are included.

Examples of the inorganic halogen compound include MgCl ₂ , AlCl _3, and MnCl ₂ .

Examples of the inorganic carbonate, sulfate, and nitrate include, for example, Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ etc. are mentioned.

Examples of the hydroxide include Mg (OH) ₂ , Al (OH) ₃ , and Ca (OH) ₂ .

(Ia) The carrier material is preferably SiO ₂ .

  The particle size of the carrier is arbitrary, but the particle size distribution is preferably 1 to 3000 μm, and from the viewpoint of particle dispersibility, the particle size distribution is more preferably within the range of 10 to 1000 μm. .

  (Ia) The support material is treated with (Ib) organoaluminum as required.

  (Ib) The organoaluminum has a general formula: (—Al (R) O—) n (wherein R is a hydrocarbon group having 1 to 10 carbon atoms, and partially halogen atoms and / or RO groups) And n is the degree of polymerization, and is 5 or more, preferably 10 or more).

  Examples of (Ib) organoaluminum compounds include methylalumoxane, ethylalumoxane, and isobutylethylalumoxane, in which R is a methyl group, an ethyl group, or an isobutylethyl group.

  In addition to the above, (Ib) organic aluminum includes, for example, trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, armenylaluminum, dialkylhydroaluminum, and sesquialkylhydroaluminum.

Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum.
Examples of the dialkyl halogeno aluminum include dialkyl halogeno aluminum such as dimethyl aluminum chloride and diethyl aluminum chloride.

  Examples of the sesquialkylhalogenoaluminum include sesquimethylaluminum chloride and sesquiethylaluminum chloride.

  Examples of (Ib) organic aluminum include ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, and sesquiethylaluminum hydride.

  (Ib) The organic aluminum is preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride.

(Ic) Examples of the transition metal compound having a cyclic η-binding anion ligand include compounds represented by the following formula (7).

In the above formula (7), M is a transition metal belonging to Group 4 of the long-period periodic table having oxidation numbers of +2, +3, and +4 and having an η ⁵ bond with one or more ligands L. Titanium is preferable as the transition metal.

  L is a cyclic η-bonding anion ligand, each independently a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, or an octahydrofluorenyl group, These groups are hydrocarbon groups containing up to 20 non-hydrogen atoms, halogens, halogen-substituted hydrocarbon groups, aminohydrocarbyl groups, hydrocarbyloxy groups, dihydrocarbylamino groups, dihydrocarbylphosphino groups, silyl groups, aminosilyls Optionally having 1 to 8 substituents each independently selected from a group, hydrocarbyloxysilyl group and halosilyl group, wherein two Ls contain up to 20 non-hydrogen atoms, hydrocarbadiyl, halohydro Carbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, diladiyl, halo Diyl, it may be linked by a divalent substituent such as an aminosilane.

  Each X independently represents a monovalent anionic σ-bonded ligand having up to 60 non-hydrogen atoms, a divalent anionic σ-bonded ligand that binds to M in a divalent manner, or M and It is a divalent anion sigma-bonded ligand that binds to L each with one valence.

  X 'is each independently a neutral Lewis base coordinating compound selected from phosphines, ethers, amines, olefins, and / or conjugated dienes having 4 to 40 carbon atoms. l is an integer of 1 or 2.

  p is an integer of 0 to 2, and X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded bond that binds to M and L with one valence each. When it is a ligand, p is 1 or more less than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand that binds to M in a divalent manner, p is the formal oxidation number of M. Less than 1 + 1.

  q is an integer of 0, 1 or 2.

  (Ic) The transition metal compound having a cyclic η-bonding anion ligand is preferably a compound in which l = 1 in the above formula (7).

(Ic) As a suitable compound of the transition metal compound having a cyclic η-bonding anion ligand, a compound represented by the following formula (8) may be mentioned.

  In the above formula (8), M is titanium, zirconium or hafnium having a formal oxidation number of +2, +3 or +4, and is preferably titanium.

Each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, and each can have up to 20 non-hydrogen atoms. Further, adjacent R ³ may be cyclic by forming a bivalent derivative such as hydrocarbadiyl, diladiyl, or germanidiyl.

  Each X ″ is independently a halogen, a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X ″ having 5 carbon atoms ~ 30 neutral conjugated dienes or divalent derivatives may be formed.

Y is O, S, NR ^* or PR ^* .

Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ , or GeR ^* ₂ .

Each R ^* is independently an alkyl group having 1 to 12 carbon atoms or an aryl group.

  n is an integer of 1 to 3.

(Ic) More preferable examples of the transition metal compound having a cyclic η-bonding anion ligand include compounds represented by the following formula (9) or the following formula (10).

  In the above formulas (9) and (10), M is titanium, zirconium, or hafnium, and is preferably titanium.

Each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, and each can have up to 20 non-hydrogen atoms.

  Z, Y, X, and X 'are as described above.

  p is an integer of 0 to 2, and q is an integer of 0 or 1.

  However, when p is 2 and q is 0, the oxidation number of M is +4, and X is halogen, hydrocarbon group, hydrocarbyloxy group, dihydrocarbylamino group, dihydrocarbyl phosphide group, hydrocarbyl sulfide group, silyl group A group or a combination thereof, having up to 20 non-hydrogen atoms. When p is 1 and q is 0, the oxidation number of M is +3, and X is an allyl group, 2- (N, N-dimethylaminomethyl) phenyl group or 2- (N, N-dimethyl) -A stabilized anionic ligand selected from aminobenzyl groups, or the oxidation number of M is +4 and X is a derivative of a divalent conjugated diene, or both M and X are metallocyclopentene groups Is forming. Further, when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is a neutral conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbons Often, X ′ can contain up to 40 carbon atoms and forms a π-type complex with M.

(Ic) As a more preferable compound of the transition metal compound having a cyclic η-bonding anion ligand, a compound represented by the following formula (11) or the following formula (12) may be mentioned.

  In the above formulas (11) and (12), M is titanium.

Each R ³ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

Y is O, S, NR ^* , or PR ^* , and Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ₂ or GeR ^* ₂ .

Each R ^* is independently hydrogen, a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or a composite group thereof, and R ^* has up to 20 non-hydrogen atoms. can be, two R ^* s or Z ^* in R ^* and in Y medium R ^* may be a circular middle Z ^* as necessary.

  p is an integer of 0 to 2, and q is an integer of 0 or 1.

  However, when p is 2 and q is 0, the oxidation number of M is +4, and each X is independently a methyl group or a hydrobenzyl group. When p is 1 and q is 0, the oxidation number of M is +3 and X is a 2- (N, N-dimethyl) -aminobenzyl group, or the oxidation number of M is +4. And X is 2-butene-1,4-diyl. Further, when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

  The dienes are examples of asymmetric dienes that form metal complexes, and are actually mixtures of geometric isomers.

  (Id) An activator capable of reacting with a transition metal compound having a cyclic η-bonding anion ligand to form a complex exhibiting catalytic activity (hereinafter simply referred to as “(Id) activator”) Examples of such a compound may include a compound represented by the following formula (13).

In the metallocene supported catalyst [I], a complex formed by (Ic) a transition metal compound having a cyclic η-bonding anion ligand and the above (Id) activator is an olefin having a high catalytic activity species. Shows polymerization activity.

In the above formula (13), [L-H] ^{d +} is a proton-provided Bronsted acid and L is a neutral Lewis base.

[M _m Q _t ] ^d- is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is each independently hydride, dialkylamide. A group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms. However, Q which is a halide is 1 or less.

  m is an integer of 1 to 7, t is an integer of 2 to 14, d is an integer of 1 to 7, and t−m = d.

As a suitable compound of (Id) activator, the compound shown by following formula (14) is mentioned.

In the above formula (14), [LH] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base.

A _{[M m Q w (G u} (T-H) r) z] d- is a non-coordinating anion compatible, M is a metal or metalloid selected from Group 5 to Group 15 of the periodic table , Q are each independently a hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms. However, Q which is a halide is 1 or less.

  G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to M and T, T is O, S, NR or PR, R is a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermanium group, or Hydrogen.

  m is an integer of 1-7, w is an integer of 0-7, u is an integer of 0 or 1, r is an integer of 1-3, z is an integer of 1-8, w + z-m = d.

As a more preferred compound of the (Id) activator, a compound represented by the following formula (15) can be mentioned.

In the above formula (15), [LH] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base.

[BQ ₃ Q ^* ] ⁻ is a compatible non-coordinating anion, B is a boron atom, Q is a pentafluorophenyl group, and Q ^* has 6 to 20 carbon atoms having one OH group as a substituent. A substituted aryl group.

  Compatible non-coordinating anions include triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) phenyl (hydroxyphenyl). ) Borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5 -Di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl,) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluoro) Phenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate and the like. And tris (pentafluorophenyl) (hydroxyphenyl) borate is preferable.

  Examples of the compatible non-coordinating anion include borates in which the hydroxy group of the borate exemplified above is replaced with NHR. Here, R is preferably a methyl group, an ethyl group or a t-butyl group.

  Protonated Bronsted acids include triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium, diethylmethylammonium, dibutylmethylammonium, dibutylethylammonium, Dihexylmethylammonium, dioctylmethylammonium, didecylmethylammonium, didodecylmethylammonium, ditetradecylmethylammonium, dihexadecylmethylammonium, dioctadecylmethylammonium, diicosylmethylammonium, bis (tallowalkyl hydrogenated) methylammonium Trialkyl group-substituted ammonium cations such as N, N-dimethyla Riniumu, N, N- diethyl anilinium, N, N-2,4,6 pentamethyl anilinium, N, N- N, such as dimethyl benzyl anilinium also include such N- dialkylanilinium cations.

(Liquid promoter component [II])
The liquid promoter component [II] may be described as an organomagnesium compound [III-1] soluble in a hydrocarbon solvent represented by the following formula (16) (hereinafter simply referred to as “organomagnesium compound [III-1]”). A hydrocarbon solvent synthesized by a reaction of the compound [III-2] selected from amines, alcohols, and siloxane compounds (hereinafter sometimes simply referred to as “compound [III-2]”). It is an organic magnesium compound that is soluble in water.

In the above formula (16), ^{M 1} is a metal atom belonging to Group 1-3 of the periodic table, ^{R 4} and ^{R 5} is a hydrocarbon group having 2 to 20 carbon atoms, a, b, c, d Is a real number that satisfies the following relationship.

0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, and e × a + 2b = c + d (e is the valence of M ¹ )

  The reaction between the organomagnesium compound [III-1] and the compound [III-2] is not particularly limited, but is not limited to aliphatic hydrocarbons such as hexane and heptane and / or aromatic hydrocarbons such as benzene and toluene. The reaction is preferably performed at room temperature to 150 ° C. in an active reaction medium.

  There is no restriction | limiting in particular about the order added in reaction which manufactures a liquid promoter component, The method of adding compound [III-2] in organomagnesium compound [III-1], Organomagnesium compound to compound [III-2] Any method of adding [III-1] or adding both at the same time may be used.

  Although there is no restriction | limiting in particular about the reaction ratio of organomagnesium compound [III-1] and compound [III-2], Compound [III- with respect to all the metal atoms contained in liquid promoter component [II] synthesize | combined by reaction. The compound [III-2] is preferably added so that the molar ratio of 2] is 0.01 to 2, and more preferably 0.1 to 1.

  The liquid promoter component [II] is used as an impurity scavenger. The liquid promoter component [II] hardly reduces the polymerization activity even at a high concentration, and therefore can exhibit a high polymerization activity in a wide concentration range. Therefore, the polymerization activity of the olefin polymerization catalyst containing the liquid promoter component [II] can be easily controlled.

  The liquid promoter component [II] may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the density | concentration of liquid promoter component [II] at the time of using for superposition | polymerization, The molar concentration of all the metal atoms contained in liquid promoter component [II] is 0.001 mmol / liter or more, 10 mmol / liter. Or less, more preferably 0.01 mmol / liter or more and 5 mmol / liter or less.

  If the molar concentration is 0.001 mmol / liter or more, the effect of impurities as a scavenger can be sufficiently exhibited, and if it is 10 mmol / liter or less, the polymerization activity can be sufficiently exhibited.

  The organomagnesium compound [III-1] is an organomagnesium compound that is soluble in the hydrocarbon solvent represented by the above formula (16).

As the above formula (16), the organomagnesium compound [III-1] is shown as a complex compound of organomagnesium soluble in a hydrocarbon solvent, but (R ⁴ ) ₂ Mg and these and other metals It includes all complexes with compounds. The relational expression e × a + 2b = c + d of the symbols a, b, c, and d indicates the stoichiometry between the valence of the metal atom and the substituent.

In the above formula (16), the hydrocarbon group having 2 to 20 carbon atoms of R ⁴ and R ⁵ is an alkyl group, a cycloalkyl group or an aryl group, and is a methyl group, an ethyl group, a propyl group, or a 1-methylethyl group. A butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1,1-dimethylethyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, and an alkyl group. Preferably, it is a primary alkyl group.

For a> 0, as the metal atom M ¹ is the periodic table can be used a metal element belonging to the group consisting of first to third group is, for example, lithium, sodium, potassium, beryllium, zinc, boron, aluminum and the like Of these, aluminum, boron, beryllium and zinc are particularly preferred.

No particular limitation on the molar ratio b / a of magnesium to metal atom ^{M 1,} but preferably in the range of 0.1 to 50, more preferably in the range of 0.5 to 10.

When a = 0, the organomagnesium compound [III-1] is preferably an organomagnesium compound soluble in a hydrocarbon solvent, and R ⁴ and R ^{5 in} the above formula (16) are represented by the following three groups ( More preferably, it is any one of i), (ii), and (iii).

(I) At least one of R ⁴ and R ⁵ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ⁴ and R ⁵ are both 4 to 6 carbon atoms, and At least one is a secondary or tertiary alkyl group.

(Ii) R ⁴ and R ⁵ are alkyl groups different from each other in carbon number, preferably R ⁴ is an alkyl group having 2 or 3 carbon atoms, and R ⁵ is an alkyl group having 4 or more carbon atoms. is there.

(Iii) R at least one of ⁴ and R ⁵ are hydrocarbon groups having 6 or more carbon atoms, preferably R ⁴ and R ⁵ are both an alkyl group having 6 or more carbon atoms.

  Examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (i) include 1-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 1-ethylpropyl group, 1, Examples include 1-dimethylpropyl group, 1-methylpentyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylpropyl group, and the like, and 1-methylpropyl group is preferable.

  Examples of the alkyl group having 2 or 3 carbon atoms in (ii) include an ethyl group and a propyl group, and an ethyl group is preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group, and an octyl group, and a butyl group and a hexyl group are preferable.

  Examples of the hydrocarbon group having 6 or more carbon atoms in (iii) include a hexyl group, an octyl group, a decyl group, a phenyl group, and the like. An alkyl group is preferable, and a hexyl group is more preferable.

  As the organomagnesium compound [III-1], increasing the number of carbon atoms of the alkyl group generally makes it easier to dissolve in a hydrocarbon solvent, but the solution tends to increase in viscosity, and an unnecessarily long alkyl group should be used. May be undesirable in handling. Although the organomagnesium compound [III-1] is used as a hydrocarbon solution, the solution may contain a slight amount of a complexing agent such as ether, ester, amine or the like, and the complex may be contained in the solution. Even if the agent remains, it can be used without any problem.

  Compound [III-2] is a compound belonging to the group consisting of an amine, an alcohol, and a siloxane compound.

  The amine compound is not particularly limited, and examples thereof include aliphatic, alicyclic or aromatic amines.

  Examples of amine compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, aniline. N-methylaniline, N, N-dimethylaniline, toluidine and the like.

  The alcohol compound is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,1-dimethylethanol, pentanol, hexanol, 2-methylpentanol, 2 -Ethyl-1-butanol, 2-ethyl-1-pentanol, 2-ethyl-1-hexanol, 2-ethyl-4-methyl-1-pentanol, 2-propyl-1-heptanol, 2-ethyl-5 -Methyl-1-octanol, 1-octanol, 1-decanol, cyclohexanol, phenol are mentioned, and 1-butanol, 2-butanol, 2-methyl-1-pentanol and 2-ethyl-1-hexanol are preferable.

  Although there is no restriction | limiting in particular as a siloxane compound, The siloxane compound which has a structural unit shown by following formula (17) is mentioned.

The siloxane compound can be used in the form of a dimer or higher chain or cyclic compound composed of one type or two or more types of structural units.

In the formula (17), R ⁶ and R ⁷ are groups selected from the group consisting of hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, or a substituted hydrocarbon group having 1 to 40 carbon atoms.

  The hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, but is a methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1 , 1-dimethylethyl group, pentyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and vinyl group. The substituted hydrocarbon group having 1 to 40 carbon atoms is not particularly limited, and examples thereof include a trifluoropropyl group.

  As siloxane compounds, symmetrical dihydrotetramethyldisiloxane, hexamethyldisiloxane, hexamethyltrisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, cyclic methylhydropentasiloxane, cyclic dimethyltetrasiloxane, cyclic methyltrifluoropropyl Tetrasiloxane, cyclic methylphenyltetrasiloxane, cyclic diphenyltetrasiloxane, (terminal methyl-capped) methylhydropolysiloxane, dimethylpolysiloxane, (terminal methyl-capped) phenylhydropolysiloxane, and methylphenylpolysiloxane are preferred.

(High pressure low density polyethylene (β))
The high pressure method low density polyethylene (β) (sometimes referred to as high pressure method low density polyethylene) that is preferably used in the polyethylene resin composition for blow molding of the present invention is an ethylene homopolymer or ethylene and one or two of them. It is preferable that it is a copolymer with the above C3-C20 alpha olefin, and can be obtained by the well-known high-pressure radical polymerization method.

The density of the high-pressure low-density polyethylene used in the present embodiment (beta) is preferably from 910~930kg / ^{m 3,} more preferably from 915~928kg / ^{m 3.} The density of the high-pressure method low-density polyethylene (β) can be measured by the method described in Examples below. Moreover, the density of the high-pressure method low-density polyethylene (β) in the resin composition can be measured by fractionating the high-pressure method low-density polyethylene by a method such as a cross fractionation chromatography method (CFC method).
The MFR of the high-pressure low-density polyethylene (β) used in the present embodiment is preferably 0.1 to 10 g / 10 minutes, and more preferably 1.0 to 5 g / 10 minutes. The MFR of the high-pressure method low-density polyethylene (β) can be measured by the method described in Examples below. Further, the MFR of the high-pressure low-density polyethylene (β) in the resin composition can be determined from the blending ratio of the MFR of the resin composition and the high-pressure low-density polyethylene.

The occupation ratio of the component having a converted molecular weight of 10 ⁶ or more of the high-pressure method low-density polyethylene (β) used in the present embodiment is determined in the gel permeation chromatography method, and preferably 1.5 to 9.0% by mass. More preferably, it is 2.5-8.5 mass%, More preferably, it is the range of 4.0-8.0 mass%. Such a high-pressure low-density polyethylene (β) having a high molecular weight component can be obtained by radical polymerization of ethylene in an autoclave type reactor.
If the high molecular weight low density polyethylene (β) component occupancy ratio of 10 ⁶ or more is within the above range, there are many branched side chains of the high pressure low density polyethylene (β) and the branch point is the starting point. It is estimated that the linear polyethylene (α) crystallizes to form a network structure in the linear polyethylene (α) and the high-pressure low-density polyethylene (β) during blow molding. Therefore, a blow molding polyethylene resin composition excellent in blow molding processability and a blow container having a good molding appearance can be obtained.
In particular, if the occupation ratio of the component having a converted molecular weight of 10 ⁶ or more of the high pressure method low density polyethylene (β) is 1.5% by mass or more, a blend of linear polyethylene (α) and high pressure method low density polyethylene (β) In this case, it is presumed that the linear polyethylene (α) and the high-pressure low-density polyethylene (β) can be made in a good compatibility state and the crystal state of both can be prevented from phase separation. For this reason, the polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance can be obtained.
The occupation ratio of the converted molecular weight of 10 ⁶ or more can be determined by a gel permeation chromatography method, and more specifically can be measured by the method described in the examples described later. The occupation ratio of the high-pressure method low-density polyethylene (β) in the polyethylene-based resin composition having a converted molecular weight of 10 ⁶ or more can also be measured by a method such as a cross-fractionation chromatography method (CFC method).
The high-pressure low-density polyethylene (β) having such characteristics can be obtained by radical polymerization of ethylene in an autoclave-type reactor, has a higher occupation ratio of 10 ⁶ or more in terms of the above-mentioned molecular weight, and has branched side chains. There are many more. By using this, it is possible to easily obtain a blown polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molded appearance.

  The high-pressure process low-density polyethylene (β) may be a copolymer of ethylene and other α-olefin, vinyl acetate, acrylate ester or the like as long as the object of the present invention is not impaired.

The polyethylene resin composition for blow molding of the present embodiment is a resin composition composed of linear polyethylene (α) as described above and high-pressure method low density polyethylene (β). Such a linear polyethylene (α) having a narrow molecular weight distribution and an occupancy of a converted molecular weight of 10 ⁶ or more that can be determined by gel permeation chromatography method are as large as 1.5 to 9.0% by mass, and are branched. A polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molding appearance, by polymer blending with a high-pressure low-density polyethylene (β) having many side chains Can be easily obtained.

  In general, blend systems of high-density polyethylene and low-density polyethylene are incompatible, and the crystalline state of the two phase-separates (for example, see Non-Patent Document 2), so blend high-density polyethylene and low-density polyethylene. In general, the blown processability of the composition is poor.

However, the molecular weight distribution Mw / Mn is as narrow as 3-7, linear polyethylene (α) having a uniform molecular weight, and an occupancy ratio of 10 ⁶ or more, which can be obtained by gel permeation chromatography, In a preferred embodiment in which a high-pressure method low-density polyethylene (β) having a large amount of 1.5 to 9.0% by mass and having many branched side chains is blended in a predetermined ratio range, the crystallization rate is increased. At the same time, a tendency that the crystal size becomes smaller and the crystal state becomes uniform is recognized, suggesting that the linear polyethylene (α) and the high-pressure method low-density polyethylene (β) are co-crystallized in a compatible state. Along with such a phenomenon, a tendency to improve the blow molding processability of the blow container containing the polyethylene resin composition for blow molding is recognized. These tendencies are more prominent when the blend amount of the high-pressure low-density polyethylene (β) is about 20% by mass with the linear polyethylene (α) as the base resin.

A known additive can be added to the polyethylene resin composition for blow molding of the present invention as necessary within a range not impairing the object of the present invention, but it is preferably essentially non-added. Polyethylene polymerized with a Ziegler-Natta catalyst requires a neutralizing agent to supplement chlorine and an antioxidant as a heat stabilizer. Examples of the neutralizing agent include metal salts of higher fatty acids such as calcium stearate and zinc stearate and hydrotalcites. Antioxidants include phenolic stabilizers and organic phosphite stabilizers. All of them are eluted in high-purity chemicals and cause contamination. Polyethylene polymerized with a metallocene catalyst is preferable because it does not require these neutralizing agents and antioxidants and can be used in blow molded articles without addition. That is, it is preferable that the blow molded article including the polyethylene resin composition for blow molding of the present embodiment substantially does not contain any of the neutralizing agent and the antioxidant that cause dust generation. Here, “substantially does not contain” means that these are not intentionally added, and specifically means that they are two or more orders of magnitude lower than the upper limit of the following addition amount.
Although it is essentially preferable to add no additives, it is preferably 150 ppm or less, more preferably 100 ppm or less as a neutralizing agent depending on the type of chemical in the contents. The antioxidant is preferably 800 ppm or less, more preferably 300 ppm or less.
It is most preferable to add a metal salt of a higher fatty acid as a neutralizing agent, which acts as a lubricant in molding processability, and the surface state of the blow molded article is relatively good.
It is most preferable to add a phenolic antioxidant as the antioxidant, which can prevent oxidative degradation due to resin chemicals and suppress discoloration and degradation of the container.

  Examples of the phenol-based stabilizer include 2,6-di-t-butyl-4-methylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6- Di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6- t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, Tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate) methane, 2,2-methyle Bis (4-methyl-6-tert-butylphenol), 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 4,4-thiobis (3-methyl-6-tert-butylphenol), 2,2 -Thiobis (4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, 3,5-tris (2-methyl-4-hydroxy-5-tert-butylphenol) methane, tetrakis (methylene (3,5-di-butyl-4-hydroxyphenyl) propionate) methane, β- (3,5- Di-t-butyl-4-hydroxylphenol) propionic acid alkyl ester, 2,2-oxamide bis (ethyl-3- (3,5-di-t-butyl-4-hydride) Loxyphenyl) propionate, tetrakis (methylene (2,4-di-t-butyl-4-hydroxyl) propionate), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-p-cresol, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzylthiono-1,3,5-triazine, 2,2 -Methylenebis (4-methyl-6-tert-butylphenol), 4,4-methylenebis (2,6-di-tert-butylphenol), 2,2-methylenebis (6- (1-methylcyclohexyl) -p-cresol) Bis (3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid) glycol ester, 4,4-butylidenebis (6-tert-butyl) Ru-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-) 4-t-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 1,3,5-tris ((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanurate, 2 -Octylthio-4,6-di (4-hydroxy-3,5-di-t-butyl) phenoxy-1,3,5-triazine, 4,4-thiobis (6-t-butyl-m-cresol), etc. Raised It is.

  Examples of organic phosphite stabilizers include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite. , Tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4- Hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite , Tris (mono or dinonylphenyl) Phosphite, hydrogenated-4,4-isopropylidenediphenol polyphosphide, bis (octylphenyl) bis (4,4-butylidenebis (3-methyl-6-tert-butylphenol)) 1,6-hexaneol diphos Phosphide, phenyl-4,4-isopropylidenediphenol pentaerythritol diphosphide, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphide, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphide, tris ((4,4, -isopropylidenebis (2-t-butylphenol)) phosphide, di (nonylphenyl) pentaerythritol diphosphide, tris (1,3-di- Stearoyloxyisopropyl) phosphite, 4,4- Sopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphide, 9,10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-) t-butylphenyl) -4,4-biphenylene diphosphide and the like.

  Organic thioester stabilizers include dialkylthiopropionates such as dilauryl-, dimyristyl-, distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (for example, glycerin, Esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate), specifically, dilauryl thiopropionate, dimyristyl thiopropionate, distearyl thiodipropionate, Examples include lauryl stearyl thiodipropionate, distearyl thiodibutyrate, and pentaerythritol tetralauryl thiopropionate.

  Stabilizers as metal salts of higher fatty acids include, for example, alkalis such as magnesium, calcium, and barium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, caprylic acid, arachidic acid, palmitic acid, and behenic acid. Earth metal salts, cadmium salts, zinc salts, lead salts, sodium salts, potassium salts, lithium salts, and the like are used.

Specific examples of stabilizers as metal salts of higher fatty acids include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate calcium oleate, barium stearate, barium laurate, barium laurate, and zinc stearate. Zinc oleate, zinc stearate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, and calcium 12-hydroxystearate.
Examples of inorganic fillers and antiblocking agents include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, and examples of lubricants include higher fatty acid amides such as stearic acid amide. .
Furthermore, examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester, and examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, and oxamides. .

  The polyethylene resin composition for blow molding of the present invention can be preferably produced by polymer blending linear polyethylene (α) and high pressure method low density polyethylene (β) using a known method.

  Examples of the polymer blending method include a melt mixing method using a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, a heated roll kneader, and the like.

  As a method of adding the above-mentioned various additives to the polyethylene resin composition for blow molding, when mixing linear polyethylene (α) and branched high-pressure method low-density polyethylene (β), various additives are directly added in advance. Examples include the method of mixing directly with linear polyethylene (α) or branched high-pressure low-density polyethylene (β), and mixing linear polyethylene (α) with branched high-pressure low-density polyethylene (β). A method of preparing a masterbatch by mixing various high-concentration additives together with linear polyethylene (α) or branched high-pressure low-density polyethylene (β) in advance, and dry-blending this at the time of molding Can also be adopted.

  Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. The measurement method and the evaluation method used in this embodiment are as follows.

(1) Density The density was measured according to JIS-K-7112: 1999.

(2) Melt flow rate (MFR)
Measured according to JIS-K-7210: 1999 (temperature = 190 ° C., load = 2.16 kg).

(3) using the apparatus of occupancy Waters Co. ALLIANCE GPCV 2000 of Mw / Mn (molecular weight distribution) and in terms of molecular weight 10 ⁶ or more component by gel permeation chromatography, Shodex manufactured by AT-807S and Tosoh as column Using TSK-gelGMH-H6 manufactured in series, the measurement by gel permeation chromatography was performed. The measurement was performed at 140 ° C. using trichlorobenzene containing 10 ppm of Irganox 1010 as a solvent. A calibration curve was prepared using commercially available monodisperse polystyrene as a standard substance.

(4) Melting point peak by differential scanning calorimeter (° C)
Using a differential scanning calorimeter (Pyris type 1 DSC device manufactured by Perkin Elmer), the measurement was performed under the following conditions. 1) About 5 mg of a polymer sample was packed in an aluminum pan, heated to 200 ° C. at 200 ° C./min, and held at 200 ° C. for 5 minutes. 2) Next, the temperature was decreased from 200 ° C. to 50 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. 3) Next, the temperature was raised from 50 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. The maximum temperature at the melting peak position was determined as the melting point peak (° C.) from the endothermic curve observed in the process of 3).
(5) Strain hardening property It measured with the following method.
Equipment: ARES manufactured by TA Instruments
Jig: Ext. Viscosity Fixture (EVF) Elongation Viscosity Measurement Jig Measurement Temperature: 134 ° C
Strain rate: 0.5 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and thickness 0.7 mm is formed by press molding.
(Calculation method)
The elongational viscosity at a strain rate of 0.5 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line, and the sudden rise phenomenon of the extension viscosity ηE is used as an index of strain hardening property. FIG. 1 is an example of a plot of elongational viscosity.
(6) Blow molding processability Using a Plako SB55 blow molding machine, die diameter 21φ / 16φ, temperature setting is cylinder 1, 2, 3, adapter, die 1, 2 in order of 160 ° C, 180 ° C, 190 ° C, 200 The temperature was 200 ° C, 200 ° C. A 500 ml round bottle was molded to confirm moldability such as bottle shapeability, bottle pinch-off fusing property, and fleshiness. As for the fleshiness, ◯ indicates that the meat circumference is good and the bottle bottom corner has a sufficient thickness, and △ indicates that the meat circumference is poor and the bottle bottom corner thickness is thin. A bottle having a hole at the time of pinch-off fusion was evaluated as x.
(7) Molding appearance (skin roughness)
Using a Plako SB55 blow molding machine, die diameter 21φ / 16φ, temperature setting is cylinder 1, 2, 3, adapter, die 1, 2 in order of 160 ° C, 180 ° C, 190 ° C, 200 ° C, 200 ° C, 200 ° C. The die head heater was turned off. The parison was extruded with a clearance of 0.5 mm and a screw rotation speed of 75 rpm, and the rough surface of the parison surface was observed. A sample having a smooth parison surface was evaluated as ◯, a sample having fine irregularities was evaluated as Δ, and a sample having a large stripe pattern was evaluated as ×.
<Resin sample preparation>
・ Linear polyethylene (α)
[Preparation of metallocene supported catalyst [I]]
Silica P-10 [manufactured by Fuji Silysia Ltd. (Japan)] was calcined at 400 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of surface hydroxyl groups of dehydrated silica was 1.3 mmol / g-SiO ₂ . 40 g of this dehydrated silica was placed in an autoclave having a capacity of 1.8 liters, and 800 cc of hexane was added and dispersed to obtain a slurry. While the obtained slurry was kept at 50 ° C. with stirring, 60 cc of a hexane solution of triethylaluminum (concentration 1 mol / liter) was added, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica to be treated with triethylaluminum. A component [IV] containing silica and a supernatant liquid and having all surface hydroxyl groups of the silica treated with triethylaluminum capped with triethylaluminum was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 800 cc of a hexane slurry of silica treated with triethylaluminum.

On the other hand, 200 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added to Isopar E [exon. Product name of hydrocarbon mixture manufactured by Chemical Co. (USA)] 1 mol of a composition formula AlMg ₆ (C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) ₁₂ dissolved in 1000 cc and previously synthesized from triethylaluminum and dibutylmagnesium 20 cc / liter hexane solution was added, and further hexane was added to adjust the titanium complex concentration to 0.1 mol / liter to obtain component [V].

  Further, 5.7 g of bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as “borate”) was added to 50 cc of toluene and dissolved, and borate Of 100 mmol / liter of toluene was obtained. 5 cc of a 1 mol / liter hexane solution of ethoxydiethylaluminum was added to this toluene solution of borate at room temperature, and further hexane was added so that the borate concentration in the solution was 70 mmol / liter. Then, it stirred at room temperature for 1 hour and obtained the reaction mixture containing a borate.

  46 cc of this reaction mixture containing borate was added to 800 cc of the slurry of component [IV] obtained above with stirring at 15 to 20 ° C., and the borate was supported on silica by physical adsorption. Thus, a slurry of silica carrying borate was obtained. Further, 32 cc of the component [V] obtained above was added and stirred for 3 hours to react the titanium complex with borate. Thus, a metallocene-supported catalyst [I] containing silica and a supernatant liquid and having catalytically active species formed on the silica was obtained.

[Preparation of liquid promoter component [II]]
Organomagnesium compounds as _[III-1], using an organic magnesium compound represented by the _{AlMg 6 (C 2 H 5)} 3 (n-C 4 H 9) 12. Methyl hydropolysiloxane (viscosity 20 centistokes at 25 ° C.) was used as compound [III-2].

To a 200 cc flask, 40 cc of hexane and AlMg ₆ (C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) ₁₂ were added with stirring while adding 37.8 mmol of Mg and Al, and methylhydropolysiloxane was added at 25 ° C. Liquid promoter component [II] was prepared by adding 40 cc of hexane containing 2.27 g (37.8 mmol) with stirring, and then raising the temperature to 80 ° C. and reacting with stirring for 3 hours.

[Preparation of ethylene homopolymer as linear polyethylene (α)]
The metallocene-supported catalyst [I] and the liquid promoter component [II] obtained above are brought into contact with hydrogen by supplying a necessary amount of hydrogen as a chain transfer agent to the catalyst transfer line and introduced into the polymerization reactor, Hexane was used as the solvent and ethylene was used as the monomer. The reaction temperature was 78 ° C., and a mixed gas of ethylene and hydrogen (the gas composition was adjusted so that the molar ratio of hydrogen to ethylene + hydrogen could be maintained at 0.0032) with a total pressure of 0.8 MPa and linear polyethylene (α The ethylene homopolymer was polymerized. The resulting ethylene homopolymer, linear polyethylene (α), has a density of 958 kg / m ³ , an MFR of 1.0 g / 10 min, and a molecular weight distribution determined by gel permeation chromatography (Mw / Mn). Was 4.0.

[Preparation of ethylene polymer as high-pressure low-density polyethylene (β)]
High pressure low density polyethylene (β-i) is obtained by radical polymerization of ethylene in an autoclave type reactor. The polymerization conditions are set to a temperature of 200 to 300 ° C. and a polymerization pressure of 100 to 250 MPa in the presence of peroxide, and a density obtained by a gel permeation chromatograph with a density of 918 kg / m ³ , MFR 2.0 g / 10 min. A high-pressure low-density polyethylene (β) having an occupancy ratio of 10 ⁶ or more in molecular weight of 8.3% by mass was obtained.

[Example 1]
100 parts by mass of a polyethylene resin composition for blow molding mixed in a proportion of 80% by mass of linear polyethylene (α) and 20% by mass of branched high-pressure low-density polyethylene (β) was TEX-44 (manufactured by Nippon Steel Works). Using a twin screw extruder having a screw diameter of 44 mm and L / D = 35), the mixture was melt kneaded and granulated at a temperature of 220 ° C. The obtained polyethylene resin composition for blow molding had a density of 950 kg / m ³ , an MFR of 0.7 g / 10 min, and a single melting point peak of 135.3 ° C. Strain hardening is observed,
With respect to this polyethylene resin composition for blow molding, the blow molding processability was evaluated as ◯ because the meat circumference was good and the thickness of the bottle bottom corner was sufficient.
The molded appearance (skin roughness) was evaluated as “good” because the parison surface was smooth.

[Comparative Example 1]
Density 958 kg / m ³ , MFR 1.0 g / 10 min, molecular weight distribution: only linear polyethylene (α) having Mw / Mn of 4.0, except not blending branched high-pressure low-density polyethylene (β) Was carried out in the same manner as in Example 1, but no blow container was obtained. Strain hardenability was not observed.

  The present invention relates to a polyethylene resin composition for blow molding excellent in blow molding processability and a blow container having a good molding appearance, and more specifically, food containers such as detergent bottles, beverage bottles, and edible oil bottles. It is suitable for large containers such as drums and industrial cans, fuel containers such as kerosene cans and gasoline tanks.

Claims (4)

It contains 85 to 65% by mass of linear polyethylene (α) and 15 to 35% by mass of high-pressure low-density polyethylene (β), and has one melting point peak on the endothermic curve obtained in the temperature rise measurement with a differential scanning calorimeter. The melt flow rate at a density of 930 to 960 kg / m ³ , 190 ° C. and a load of 2.16 kg is 0.1 to 2.0 g / 10 minutes, and has strain hardening in the measurement of elongational viscosity. A polyethylene resin composition for blow molding characterized in that the linear polyethylene (α) satisfies the following requirements (α-1) to (α-4), and the high-pressure low-density polyethylene: (Β) satisfies the following requirements (β-1) to (β-3): The polyethylene resin composition for blow molding described above .
(Α-1) An ethylene homopolymer or a copolymer comprising a repeating unit derived from ethylene and a repeating unit derived from one or two or more α-olefins having 3 to 20 carbon atoms.
(Α-2) The density is 935 to 975 kg / m ³ .
(Α-3) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 min.
((Alpha) -4) Mw / Mn calculated | required by the gel permeation chromatography method is 3-7.
(Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mw / Mn is an index representing a molecular weight distribution.)
(Β-1) The density is 910 to 930 kg / m ³ .
(Β-2) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 10 g / 10 min.
(Β-3) The occupation ratio of the component having a converted molecular weight of 10 ⁶ or more determined by gel permeation chromatography is 1.5 to 9.0% by mass of the whole high-pressure method low-density polyethylene (β). Wherein the linear polyethylene (alpha), (A) a carrier material, (b) an organoaluminum, (c) a transition metal compound having a cyclic η binding anionic ligands, and (d) the cyclic η binding anion distribution ligand metallocene supported catalyst [I] prepared from the transition metal compound reacted with the complex capable of forming an activator which express catalytic activity with, produced by polymerization using a liquid cocatalyst component [II] characterized by having a step, the manufacturing method of the blow molding polyethylene resin composition of claim 1. A blow molded article comprising the polyethylene resin composition for blow molding according to claim 1 . The blow molded product according to claim 3 , which is a container.